CN103117107B - Form the compositions of electrode of solar battery, method and the solaode of this electrode of use - Google Patents

Form the compositions of electrode of solar battery, method and the solaode of this electrode of use Download PDF

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CN103117107B
CN103117107B CN201210443825.1A CN201210443825A CN103117107B CN 103117107 B CN103117107 B CN 103117107B CN 201210443825 A CN201210443825 A CN 201210443825A CN 103117107 B CN103117107 B CN 103117107B
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weight
electrode
dispersion
metal
nano silver
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CN103117107A (en
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林年治
高田佳明
山崎和彦
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Mitsubishi Materials Corp
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Priority claimed from JP2006305409A external-priority patent/JP5070808B2/en
Priority claimed from JP2006305508A external-priority patent/JP5309440B2/en
Priority claimed from JP2006307307A external-priority patent/JP5248006B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

The present invention provides the composition for electrode formation of solaode; said composition is the composition for electrode formation that metal nanoparticle is scattered in the solaode of disperse medium; described metal nanoparticle contains the Nano silver grain of more than 75 weight %; described metal nanoparticle is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 1～3, and the primary particle size that described metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm.

Description

Form the compositions of electrode of solar battery, method and the solaode of this electrode of use
The application be international filing date be on March 20th, 2007, international application no be PCT/JP2007/055649, the Application No. 200780031764.5 entering thenational phase, the divisional application of PCT application of invention entitled " solaode of the electrode that the composition for electrode formation of solaode and the forming method of this electrode and use utilize this forming method to obtain ".
Technical field
The present invention relates to the solaode of the electrode that the compositions of the electrode for forming solaode, the method using said composition formation electrode and use utilize this forming method to obtain.The invention still further relates to form the method for the electrode of solaode and use the solaode of the electrode utilizing this forming method to obtain.
This application claims on the June 30th, 2006 of the Patent 2006-181818 in Japanese publication, Patent 2006-277230 filed in 11 days October in 2006, Patent 2006-288528 filed in 24 days October in 2006, Patent 2006-288529 filed in 24 days October in 2006, Patent 2006-288530 filed in 24 days October in 2006, Patent 2006-305409 filed in 10 days November in 2006, Patent 2006-305508 filed in 10 days November in 2006, the priority of Patent filed in 14 days November in 2006 2006-307307, quote its content in this article.
Background technology
In the past, forming method as the electrode of solaode, disclose the metal electrode forming method of following solaode: burn till the solution of the low-molecular-weight organic solvent that the ultrafine metal particle of the following 0.03 following particle diameter of μm is scattered in 100～about 200 by coating on opto-electronic conversion semiconductor layer, and form lower electrode layers, on opto-electronic conversion semiconductor layer, to burn till the solution used with the formation with above-mentioned lower electrode layers identical in coating, or weight concentration more higher than the solution that the formation of lower electrode layers is used contains the solution of ultrafine metal particle, and form upper electrode layer (such as, patent documentation 1: patent the 3287754th is (with reference to claim 1, paragraph [0024], paragraph [0035])).In this metal electrode forming method, after ultrafine metal particle being dispersed with by silk screen print method etc. and the solution that viscosity adjustment is about 10000cps is coated on opto-electronic conversion semiconductor layer, keep more than 30 minutes at a temperature of 100～250 DEG C, preferably 250 DEG C and burn till, form metal electrode (lower electrode layers or upper electrode layer).
In the metal electrode forming method of the solaode so constituted, opto-electronic conversion semiconductor layer is coated with after ultrafine metal particle is scattered in the solution of organic solvent, sinter in a low temperature of 100～250 DEG C, the most do not use fine vacuum technique i.e. can obtain having high reflectance and conductivity and large-area metal electrode.
Additionally, as the compositions used in the forming method of the electrode of solaode, disclose conductive composition used for solar batteries, it is characterized in that, comprise Ag powder, and the metal of at least one in V, Mo, W or its compound, frit, with organic carrier (such as, patent documentation 2: Unexamined Patent 10-326522 (with reference to claim 2, paragraph [0022], paragraph [0031])).In above-mentioned patent documentation 2, the substrate being printed with this conductive composition used for solar batteries is burnt till 5 minutes formation Ag electrodes in 550 DEG C.By using the conductive composition used for solar batteries shown in patent documentation 2, the agglutinating property of Ag electrode can be remarkably promoted.The electric conductivity of electrode under the easy fired of less than 700 DEG C, film-strength can be improved especially, can help to cost degradation that low-temperature firing brings, the treatment temperature of base component has electrode during ceiling restriction to be formed.
Also disclose a kind of electrocondution slurry, it is complexed metal powder, oxide powder and the electrocondution slurry of carrier, it is characterized in that, metal dust is the metal dust of at least one in Ag, Cu and Ni, oxide powder is by least one in Bi, Fe and Ag, the crystalline composite oxide power (for example, referring to patent documentation 3: Unexamined Patent 11-329070 (claims 1 to 3, paragraph [0009], paragraph [0031])) constituted with at least one in periodic chart V group element, VI race element.In above-mentioned patent documentation 3, the silicon chip being printed with electrocondution slurry is burnt till at maximum temperature 750 DEG C and forms electrode.With the electrocondution slurry shown in this patent documentation 3, the electrode that contact resistance is low, adhesive strength is big can be reliably formed.
Additionally, disclose the forming method of a kind of solar cell device, this forming method forms the region in other conductivity types in an interarea side of the semiconductor substrate in monopole type, an interarea side at this semiconductor substrate forms antireflection film simultaneously, on this antireflection film, other interarea sides calcining with semiconductor substrate comprises silver powder, organic carrier and the electrode material of frit, it is characterized in that, on antireflection film, the electrode material of calcining contains Ti, Bi, Co, Zn, Zr, Fe, in Cr composition at least one or multiple (such as, with reference to patent documentation 4: No. 2001-313400 (claim 1 of JP, paragraph [0027], paragraph [0039])).In above-mentioned patent documentation 4, calcine slurry at 700 DEG C and form solar cell device.According to the method shown in patent documentation 4, though from antireflection film coating electrode material and calcine, it is possible to obtain that Ohmic contact (Fill factor) is good, solar cell device that tractive intensity is big.
As the method using the raw material containing metal microparticle such as conductive paste to form metal electrode on a semiconductor substrate, disclose coating in the past and contain the particle shape silver compounds such as silver oxide, Disilver carbonate, silver acetate and reducing agent and the conductive composition of binding agent, heat and form the method (for example, referring to patent documentation 5: No. 2003/085052 pamphlet of International Publication (claims 1 to 3, claim 11, page 3 the 32nd row～33 row)) of conductive cell envelope.According to patent documentation 5, even if not against the membrance casting condition of high temperature, it is also possible to obtain the low specific insulation of the argent that is equal to, the conductive cell envelope of high conductivity.
Additionally, for containing organic bond, solvent, frit, conductive paste with electroconductive powder, disclose containing selected from Ti, Bi, Zn, Y, the metal of at least one in In and Mo or the powder of its metallic compound, its mean diameter is the above conductive paste less than 0.1 μm of 0.001 μm, with by this conductive paste printing or burn till after being coated on the anti-reflection layer of silicon semiconductor and manufacture the method for solaode (such as, with reference to patent documentation 6: JP 2005-243500 public affairs (claim 1, claim 6, paragraph [0021]).).For the conductive paste shown in above-mentioned patent documentation 6, it is preferable for being burnt till and form electrode at a temperature of 550～850 DEG C by the substrate being printed with or being coated with this conductive paste.According to patent documentation 6, the additive of ultramicron is uniformly dispersed, is burnt till, thus can be formed and there is between quasiconductor and conductive paste via anti-reflection layer existence stable high conduction and the surface electrode of excellent bonding force.
Summary of the invention
In the metal electrode forming method of the solaode shown in above-mentioned existing patent documentation 1; in order to make the ultrafine metal particle stabilisation in the metal electrode after burning till; must be while guaranteeing the electric conductivity of regulation, the low-molecular-weight organic matter with 100～about 200 protects ultrafine metal particle.On the other hand, in order to make to be scattered in the ultrafine metal particle sinteringization of organic solvent at low temperatures, if reducing the size of this ultrafine metal particle, then the specific surface area of ultrafine metal particle increases, and the ratio shared by above-mentioned Organic substance increases.For this, in the metal electrode forming method of the solaode shown in above-mentioned existing patent documentation 1, it is scattered in the low-temperature sintering of the ultrafine metal particle of organic solvent, if not making the desorbing due to heat of above-mentioned Organic substance, or decompose (segregated combustion), just cannot realize, particularly when carry out burning till below 220 DEG C and the metal electrode that obtains carries out atmospheric exposure test for being scattered in the ultrafine metal particle of organic solvent, if specifically housing metal electrode 1000 hours in keeping the constant temperature and humidity cabinet that temperature is 100 DEG C and humidity is 50%, the most above-mentioned Organic substance is rotten or aging, the conductive problem with reflectance reduction.
As shown in above-mentioned patent documentation 2～4, in the case of base material is silicon substrate or ceramic substrate, glass substrate, in order to improve the adhesive strength for base material and use frit or the high temperature with its alternative material burn till the thick film ink of type, the film that dhering strength is high can be formed.But, formed electrode as shown in above-mentioned patent documentation 2～4 compositions must more than 500 DEG C at a temperature of burn till, have the problem damaging base material at the temperature disclosed above.
During it addition, use the polymeric substrates such as organic polymer as base material, in order to improve the conductive adhesive of adhesive strength also use organic system bonding agent, use the thick film ink of the low temperature polymer type of organic bond.The slurry of the type due to less than 200 DEG C burn till, binding agent generation thermal contraction, contacted with each other acquisition conduction by the conductive particle contained.But owing to being mingled with the reasons such as binding agent as insulant between particle, the contact resistance composition between conductive particle is big, and the specific insulation of the electrode of formation is high, has the problem resting on low conductivity.
As the forming method of the electrode of solar system battery, in the method shown in above-mentioned patent documentation 5, although the electrode comprising the metal tunicle with the specific insulation close to reguline metal can be obtained, but be difficult to obtain the tunicle high with the adaptation of base material.
In method shown in above-mentioned patent documentation 6, frit must melt, therefore must burn till at a temperature of the softening temperature of the pyrex enumerated as representational frit, i.e. more than 300 DEG C, in patent documentation 6, preferred firing temperature is the highest, when such as engaging with non-crystalline silicon base material used for solar batteries, make the dysgenic problems such as conversion efficiency deterioration.Owing to being the firing temperature of the heat resisting temperature exceeding most resinaes, it is difficult to the substrate applications with resinae as substrate.
It is an object of the invention to, it is provided that also can maintain high conductivity and high reflectance even if using all the year round, the electrode of excellent in stability year in year out can be obtained, the forming method of the electrode used for solar batteries of the composition for electrode formation of solaode and use said composition.
Other mesh of the present invention are, easy fired technique by 130～400 DEG C is provided, also high conductivity and high reflectance can be maintained even if using all the year round, the electrode of excellent in stability year in year out can be obtained, the solaode of the electrode that the forming method of the electrode of solaode and use are obtained by this forming method.
Other objects of the present invention are, the composition for electrode formation that provide and give above-mentioned composition adaptation further, the solaode of the electrode of excellent adhesion can be obtained in addition to above-mentioned characteristic, the forming method of electrode used for solar batteries, and use said composition, the solaode of forming method.
Other objects of the present invention are, it is not necessarily to vacuum technology when film forming is provided, there is good texture structure, and then the average surface roughness of controlled weaving structure structure, the composition for electrode formation of solaode and the forming method of this electrode and use the solaode of the electrode utilizing this forming method to obtain.
Other objects of the present invention are, it is provided that can form the forming method of electrode, the solaode electrode of the excellent adhesion with base material and the solaode of electrode that use utilizes this forming method to obtain.
Other objects of the present invention are, it is provided that can form the forming method of electrode, the solaode electrode of excellent electric conductivity and the solaode of electrode that use utilizes this forming method to obtain.
Other objects of the present invention are, it is provided that can form the forming method of high electrode, the solaode electrode of the reflectance of visible ray and the solaode of electrode that use utilizes this forming method to obtain.
1st scheme of the present invention is the composition for electrode formation that metal nanoparticle is scattered in the solaode of disperse medium; metal nanoparticle contains the Nano silver grain of more than 75 weight %; metal nanoparticle is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 1～3, and the primary particle size that metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm.
The compositions of the 1st scheme is 10～50nm larger-size metal nanoparticles due to a large amount of primary particle sizes that contain, and therefore the specific surface area of metal nanoparticle reduces, and the ratio shared by disperse medium diminishes.Therefore, if using said composition to form the electrode of solaode, desorbing or the decomposition because of heat when burning till of the organic molecule in the most above-mentioned disperse medium, or eliminate and decompose, the electrode with silver as main constituent being substantially free of organic thing can be obtained.
The forming method of the electrode that the 2nd scheme is solaode of the present invention, the method includes: is coated with engineering method by wet type on base material and is coated with the composition for electrode formation that the 1st scheme described in work is recorded, the operation making the thickness after burning till be the film forming in the range of 0.1～2.0 μm；With by the base material of the film forming above in 130～400 DEG C of operations burnt till.
In the forming method of the electrode of the solaode of the 2nd scheme; by burning till under 130～400 DEG C of low temperature; protection metal nanoparticle surface disperse medium in organic molecule desorbing decomposition or eliminate and decompose, thus can obtain the electrode with silver as main constituent being substantially free of organic thing.
3rd scheme of the present invention is the composition for electrode formation that metal nanoparticle is scattered in the solaode of disperse medium, metal nanoparticle contains the Nano silver grain of more than 75 weight %, metal nanoparticle is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 1～3, the primary particle size that metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm, compositions contains further selected from metal-oxide, metal hydroxides, one kind or two or more additive in organo-metallic compound and silicone oil.
Compositions for the 3rd scheme, compositions contains one kind or two or more additive in metal-oxide, metal hydroxides, organo-metallic compound and silicone oil further, if therefore using said composition to form the electrode of solaode, then can obtain the excellent adhesion of the electrode with silver as main constituent being substantially free of organic thing, this electrode and base material.If using said composition to form electrode, then can give the inhibition of the grain growth that the sintering between metal nanoparticle brings, therefore can form the electrode with good texture structure.The average surface roughness of the most controlled weaving structure structure.In the formation using the electrode of compositions of the present invention, being not necessarily to vacuum technology during film forming, therefore the restriction of technique is little, and the operating cost of manufacture equipment can be greatly reduced.
4th scheme of the present invention is the forming method of the electrode of solaode, the method includes: is coated with engineering method by wet type on base material and is coated with the composition for electrode formation that the 3rd scheme described in work is recorded, the operation making the thickness after burning till be the film forming in the range of 0.1～2.0 μm；With by the base material of the film forming above in 130～400 DEG C of operations burnt till.
In the forming method of the electrode of the solaode of the 4th scheme, by burning till under 130～400 DEG C of low temperature, organic molecule desorbing in the disperse medium on the surface of protection metal nanoparticle or decomposition, or eliminate and decompose, thus can obtain the electrode with silver as main constituent being substantially free of organic thing, additionally, due to compositions contains the metal-oxide as additive, metal hydroxides, organo-metallic compound or silicone oil, increase with chemical bond or the anchoring effect of base material, or metal nanoparticle improves with the wettability of base material in the firing process of 130～400 DEG C, the electrode being consequently formed and the excellent adhesion of base material.In the forming method of the 4th scheme, compositions wet type on base material being coated with work and film forming, the easy operation of the available base material burning till film forming forms electrode.So, being not necessarily to vacuum technology during film forming, the restriction of technique is little, and the operating cost of manufacture equipment can be greatly reduced.
5th scheme of the present invention is the improvement of method of the electrode forming solaode, comprising: composition for electrode formation is coated with engineering method by wet type on base material be coated with work and the operation of film forming, and the operation that the base material of the film forming above is burnt till.The composition of its feature is that base material is implemented primary coat processes.
Before in the invention of described 5th scheme, composition for electrode formation being coated with on base material work, burn till and forming electrode, the primary coat that base material is implemented to carry out primary coat processes, and thus can improve the adaptation of electrode and base material.
The forming method of the electrode that the 6th scheme is solaode of the present invention; it it is the invention that relates to of the 5th scheme; composition for electrode formation is the compositions that metal nanoparticle is scattered in disperse medium; metal nanoparticle contains the Nano silver grain of more than 75 weight %; metal nanoparticle is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 1～3, and the primary particle size that metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm.
In the invention that 6th scheme relates to, by using above-mentioned composition for electrode formation, can form, with burning till in a low temperature of less than 400 DEG C, the electrode that excellent electric conductivity, visible ray reflectance is high.
As mentioned above; according to the present invention; the Nano silver grain containing more than 75 weight % owing to being scattered in the metal nanoparticle of disperse medium; protective agent chemical modification metal nanoparticle with the organic molecule main chain that carbon skeleton is carbon number 1～3; and the primary particle size that metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm; therefore the specific surface area of the metal nanoparticle in said composition reduces relatively, and disperse medium proportion diminishes.As a result, if using said composition to form the electrode of solaode, the heat when organic molecule in above-mentioned disperse medium is owing to burning till and desorbing or decomposition or eliminate and decompose, the electrode with silver as main constituent being substantially free of organic thing can be obtained.Therefore, even if use the solaode being formed with above-mentioned electrode throughout the year, Organic substance also undergoes no deterioration or aging, and conductivity and reflectance can maintain high level, therefore can obtain the electrode of excellent in stability year in year out.
If above-mentioned composition for electrode formation being coated with engineering method by wet type on base material be coated with work; film forming be the thickness after burning till be in the range of 0.1～2.0 μm; if film forming base material on this is burnt till in 130～400 DEG C; protection metal nanoparticle surface disperse medium in organic molecule desorbing decomposition or eliminate and decompose, thus can obtain the electrode with silver as main constituent being substantially free of organic thing.As a result, same as described above, even if use the solaode being formed with above-mentioned electrode throughout the year, conductivity and reflectance can maintain high level, therefore can obtain the electrode of excellent in stability year in year out.
The composition for electrode formation of the present invention, the metal nanoparticle being scattered in disperse medium contains the Nano silver grain of more than 75 weight %, protective agent chemical modification metal nanoparticle with the organic molecule main chain that carbon skeleton is carbon number 1～3, the primary particle size that metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm, compositions contains further selected from metal-oxide, metal hydroxides, one kind or two or more additive in organo-metallic compound and silicone oil, if therefore using said composition to form the electrode of solaode, the electrode with silver as main constituent being substantially free of organic thing can be obtained, this electrode and the excellent adhesion of base material.If it addition, use said composition to form electrode, then can give the inhibition of the grain growth that the sintering between metal nanoparticle brings, therefore can form the electrode with good texture structure.It addition, the average surface roughness that texture constructs can be suppressed.In the formation using the electrode of compositions of the present invention, being not necessarily to vacuum technology during film forming, therefore the restriction of technique is little, and manufacture equipment operation cost also can be greatly reduced.
Additionally; if being coated with engineering method with wet type on base material to be coated with the above-mentioned composition for electrode formation of work and make the thickness after burning till be ground film forming in the range of 0.1～2.0 μm; the base material of film forming above this is burnt till in 130～400 DEG C; then protect metal nanoparticle surface disperse medium in organic molecule desorbing decomposition or eliminate and decompose, thus can obtain the electrode with silver as main constituent being substantially free of organic thing.As a result, same as described above, even if use the solaode being formed with above-mentioned electrode throughout the year, conductivity and reflectance also can maintain high level, therefore can obtain the electrode of excellent in stability year in year out.Additionally, due to the metal-oxide contained in the composition as additive, metal hydroxides, organo-metallic compound or silicone oil, be combined with the chemical of base material or the improvement of metal nanoparticle under the firing process of the increase of anchoring effect or 130～400 DEG C and the wettability of base material, the electrode of formation and the excellent adhesion of base material.In the forming method of the electrode of the solaode of the present invention, on base material, wet type is coated with work compositions and film forming, and the easy operation of the available base material burning till film forming forms electrode.So, being not necessarily to vacuum technology during due to film forming, the restriction of technique is little, it is also possible to the operating cost of manufacture equipment is greatly reduced.
The forming method of the electrode of the solaode of the present invention, by being coated with work composition for electrode formation on base material, burns till and base material is implemented to carry out before forming electrode the primary coat of primary coat and processes, can improve the electrode of formation and the adaptation of base material.Therefore, when base material uses conductive material, process the composition in the coating material of use, amount by adjusting primary coat, the electrode that electric interlock is excellent can be obtained.
In the forming method of the electrode of the solaode of the present invention use composition for electrode formation, be scattered in the Nano silver grain that the metal nanoparticle of disperse medium contains more than 75 weight %; protective agent chemical modification metal nanoparticle with the organic molecule main chain that carbon skeleton is carbon number 1～3; and the primary particle size that metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm; therefore the specific surface area of the metal nanoparticle in compositions reduces relatively, and disperse medium proportion diminishes.Base material is coated with engineering method with wet type and is coated with this composition for electrode formation of work; film forming is so that the thickness after burning till reaches 0.1～2.0 μm; if burning till this base material in film forming above at 130～400 DEG C; then protect metal nanoparticle surface disperse medium in organic molecule owing to burning till time heat and desorbing or decomposition or eliminate and decompose, thus can obtain the electrode with silver as main constituent being substantially free of organic thing.As a result, even if use the solaode being formed with above-mentioned electrode throughout the year, Organic substance also undergoes no deterioration or aging, and conductivity and reflectance can maintain high level, therefore can obtain the electrode of excellent in stability year in year out.Furthermore it is possible to by burning till formation electrode in a low temperature of less than 400 DEG C, the energy of consumption when electrode is formed therefore can be cut down.Furthermore, it is applicable to due to the heat resisting temperature of the semiconductor substrate burning till the used for solar batteries many silicon causing hot injury etc of more than 400 DEG C or resinae etc the low raw material base material as substrate.
Detailed description of the invention
Then explanation is for preferred embodiment of the present invention.
1st embodiment
(composition for electrode formation of solaode)
The composition for electrode formation of the solaode of the present invention is the compositions that metal nanoparticle is scattered in disperse medium.Above-mentioned metal nanoparticle contains the Nano silver grain of more than more than 75 weight %, preferably 80 weight %.The content of Nano silver grain is defined in relative to the scope that all metal nanoparticle 100 weight % are more than 75 weight %, is because less than the reflectance reduction of the electrode of the solaode of use said composition formation during 75 weight %.It addition, metal nanoparticle is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 1～3.The carbon number of the carbon skeleton of protectant organic molecule main chain of chemical modification metal nanoparticle is limited to the scope of 1～3; if being because carbon number is more than 4, because heat protective agent when burning till is difficult to desorbing or decomposes (segregated combustion); remain organic detritus in a large number in above-mentioned electrode and go bad or aging, the electric conductivity of electrode and reflectance reduction.
Metal nanoparticle contains average more than 70%, the primary particle size of preferably more than 75% is the metal nanoparticle in the range of 10～50nm.The content that primary particle size is metal nanoparticle in the range of 10～50nm is defined to average relative to the scope that all metal nanoparticles 100% are more than 70%, the specific surface area being because metal nanoparticle during less than 70% increases the change of Organic substance proportion greatly, even if heat during because burning till is prone to desorbing or decomposes the organic molecule of (segregated combustion), this organic molecule proportion is many, therefore organic detritus is remained in electrode in a large number, this residue is rotten or aging and the electric conductivity of electrode and reflectance reduction, or the particle size distribution of metal nanoparticle becomes wide, the density of electrode is easily reduced, the electric conductivity of electrode and reflectance reduction.Being limited in the range of 10～50nm by the primary particle size of above-mentioned metal nanoparticle further, being because according to statistical method primary particle size is that the metal nanoparticle in the range of 10～50nm is relevant to ageing stability (stability year in year out).
On the other hand, metal nanoparticle beyond Nano silver grain, for comprising the one kind or two or more mixing composition in Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Cr, Fe and Mn or the metal nanoparticle of alloy composition, contain more than 0.02 weight % and less than the metal nanoparticle beyond 25 weight %, preferably 0.03 weight %～this Nano silver grain of 20 weight % relative to all metal nanoparticle 100 weight %.Being defined to by the content of the metal nanoparticle beyond Nano silver grain relative to all metal nanoparticle 100 weight % is more than 0.02 weight % and the scope less than 25 weight %, although problem of less than nothing big when being because less than 0.02 weight %, but in the range of 0.02～25 weight %, there is the feature that the electric conductivity of the electrode after atmospheric exposure test (keeping the test of 1000 hours in the constant temperature and humidity cabinet of temperature 100 DEG C and humidity 50%) does not deteriorates compared with before atmospheric exposure test with reflectance, the electric conductivity of the electrode after just burning till time more than 25 weight % and reflectance reduction, and the electrode after atmospheric exposure test is than the electrode conductivity before atmospheric exposure test and reflectance reduction.
The content of the metal nanoparticle containing Nano silver grain is %2.5 relative to compositions 100 weight comprising metal nanoparticle and disperse medium～95.0 weight %, preferably 3.5～90 weight % are preferable.The content of the metal nanoparticle containing Nano silver grain is set as relative to the scope that compositions 100 weight % is 2.5～95.0 weight % comprising metal nanoparticle and disperse medium, it is because while do not have anything to affect less than characteristic on the electrode after burning till during 2.5 weight %, but be difficult to obtain the electrode of necessary thickness, if it exceeds the wet type of 95.0 weight % then compositions is coated with the necessary mobility can lost man-hour as ink or slurry.
The disperse medium of the composition for electrode formation constituting the present invention comprises alcohols or is preferable containing alcohol solution.The alcohols used as disperse medium can list, one kind or two or more in methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, isobornyl hexanol and erithritol.Contain more than the water of more than more than 1 weight %, preferably 2 weight % and 2 weight % containing alcohol solution relative to all disperse medium 100 weight %, more than preferably 3 weight % alcohols is preferable.Such as, in the case of disperse medium only comprises water and alcohols, during containing water 2 weight %, containing alcohols 98 weight %, during containing alcohols 2 weight %, containing water 98 weight %.The scope that content is more than 1 weight % of water is made relative to all disperse medium 100 weight %, when being because less than 1 weight %, it is difficult under low temperature sinter the film utilizing wet type to be coated with engineering method painting work compositions and to obtain, or the electric conductivity of the electrode after burning till and reflectance reduction, the scope that content is more than 2 weight % of alcohols is made relative to all disperse medium 100 weight %, when being because less than 2 weight %, same as described above, it is difficult under low temperature to sinter and utilizes wet type to be coated with engineering method to be coated with work compositions and the film that obtains, or the electric conductivity of the electrode after burning till and reflectance reduction.
Disperse medium, i.e. protection molecule in surfaces of metal nanoparticles chemical modification preferably comprise any one in hydroxyl (-OH) or carbonyl (-C=O) or two kinds.If the protective agent of the metal nanoparticles such as chemical modification Nano silver grain contains hydroxyl (-OH); then the dispersion stabilization of compositions is excellent; there is the low-temperature sintering for film the most effectively act on; if the protective agent of the metal nanoparticles such as chemical modification Nano silver grain contains carbonyl (-C=O); the most same as described above; the dispersion stabilization of compositions is excellent, has the low-temperature sintering for film and the most effectively acts on.
(forming method of compositions)
The manufacture method of the composition for electrode formation of the solaode that explanation is so formed below.
The situation of the Nano silver grain of the protective agent chemical modification of the organic molecule main chain that carbon number is 3 of (a) use carbon skeleton
First silver nitrate is dissolved in the water such as deionized water and modulates aqueous metal salt.On the other hand, in sodium citrate is dissolved in the water such as deionized water the sodium citrate aqueous solution of the concentration 10 obtained～40%, directly adding the granular or ferrous sulfate of powdery in the air-flow of the noble gases such as nitrogen and make it dissolve, modulation contains the reducing agent aqueous solution of citrate ions and ferrous ion with the mol ratio of 3: 2.Then while stirring above-mentioned reducing agent aqueous solution in above-mentioned inert gas flow, in this reducing agent aqueous solution, dripping above-mentioned aqueous metal salt and mix.Here, preferably by adjusting the concentration of each solution, so that less than the 1/10 of the amount that the addition of aqueous metal salt is reducing agent aqueous solution, even if the aqueous metal salt of dropping room temperature, reaction temperature also will remain in 30～60 DEG C.The mixing ratio of above-mentioned two aqueous solutions is adjusted to 3 times of the equivalent that equivalent is metal ion of the ferrous ion added as reducing agent.That is, (molal quantity of the metal ion in aqueous metal salt) × (valence mumber of metal ion)=3 × (molal quantity of the ferrous ion in reducing agent aqueous solution) it is adjusted to.After the completion of dropwise addition of aqueous metal salt, the stirring 10 of continuation mixed liquor～300 minutes, modulation comprises the dispersion liquid of metallic colloid.Ambient temperatare puts this dispersion liquid, after the agglutinator of the metal nanoparticle being separated Shen fall by decant or centrifugal separation etc., in this separator, add the water such as deionized water make dispersion, desalting processing is carried out by sucking filtration, then replacing washing with alcohols, the content making metal (silver-colored) is 2.5～50 weight %.Afterwards, the centrifugal force using centrifugal separator to adjust this centrifugal separator carrys out separating coarse-grained son, thus metal nanoparticle is adjusted to the primary particle size containing average more than 70% be the metal nanoparticle in the range of 10～50nm, to be i.e. adjusted under average relative to the primary particle size of all metal nanoparticles 100% be that the ratio shared by the metal nanoparticle in the range of 10～50nm reaches more than 70%.It should be noted that, although being recited as metal nanoparticle, but in the case of being somebody's turn to do (a), being adjusted under average relative to the primary particle size of all Nano silver grains 100% is that the ratio shared by the Nano silver grain in the range of 10～50nm reaches more than 70%.
For the assay method of average, first the metal nanoparticle TEM (Transmission Electron Microscope, transmission electron microscope) obtained is shot with the multiplying power of about about 500,000 times.Then, the image obtained metal nanoparticle 200 is measured primary particle size, based on this measurement result, make particle diameter distribution.Then, the particle diameter distribution made obtaining primary particle size is the number ratio that the metal nanoparticle in the range of 10～50nm accounts for whole metal nanoparticle.
Thus, the dispersion of the Nano silver grain being dispersed with the protective agent chemical modification by the organic molecule main chain that the carbon number of carbon skeleton is 3 can be obtained.
Then, the dispersion of acquisition is adjusted to final tenor (silver content) and accounts in dispersion 100 weight % in the range of 2.5～95 weight %.With disperse medium for during containing alcohol solution, preferably water and the alcohols of solvent are adjusted to more than 1% and more than 2% respectively.Then, this dispersion is made to contain the one kind or two or more additive in metal-oxide, metal hydroxides and organo-metallic compound further.Adjust the content of additive so that the weight of Nano silver grain reaches in the range of 1/1000～1/5.Thus by the silver nanoparticle dispersion of the protective agent chemical modification of organic molecule main chain that the carbon number of carbon skeleton is 3 in disperse medium, the composition for electrode formation of the one kind or two or more additive contained further in metal-oxide, metal hydroxides and organo-metallic compound can be obtained.
B () uses the situation of the Nano silver grain of the protective agent chemical modification by the organic molecule main chain that carbon number is 2 of carbon skeleton
The sodium citrate used during by modulation reducing agent aqueous solution replaces with natrium malicum, in addition modulates dispersion in the same manner as above-mentioned (a).Thus can obtain the dispersion of the Nano silver grain being dispersed with the protective agent chemical modification by the organic molecule main chain that the carbon number of carbon skeleton is 2.
C () uses the situation of the Nano silver grain of the protective agent chemical modification by the organic molecule main chain that carbon number is 1 of carbon skeleton
The sodium citrate used during by modulation reducing agent aqueous solution replaces with sodium glycollate, in addition modulates dispersion in the same manner as above-mentioned (a).Thus can obtain the dispersion of the Nano silver grain being dispersed with the protective agent chemical modification by the organic molecule main chain that the carbon number of carbon skeleton is 1.
The situation that carbon number is 3 of the carbon skeleton of protectant organic molecule main chain of the metal nanoparticle beyond (d) chemical modification Nano silver grain
Metal as the metal nanoparticle constituted beyond Nano silver grain can list, Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr or Mn.In addition to the silver nitrate used when by modulation aqueous metal salt replaces with gold chloride, chloroplatinic acid, Palladous nitrate., ruthenium trichloride, Nickel dichloride., cuprous nitrate, stannum dichloride, indium nitrate, zinc chloride, iron sulfate, chromic sulfate or manganese sulfate, modulate dispersion in the same manner as above-mentioned (a).It is derived from the dispersion that carbon number is 3 (composition for electrode formation of solaode) of the carbon skeleton of protectant organic molecule main chain of metal nanoparticle beyond chemical modification Nano silver grain.
It should be noted that; when the carbon number of the carbon skeleton of protectant organic molecule main chain of the metal nanoparticle beyond chemical modification Nano silver grain is 1 or 2; the silver nitrate used when by modulation aqueous metal salt replaces with in addition to the slaine of mentioned kind, modulates dispersion in the same manner as above-mentioned (b) or above-mentioned (c).Thus, the dispersion that carbon number is 1 or 2 (composition for electrode formation of solaode) of the carbon skeleton of protectant organic molecule main chain of metal nanoparticle beyond chemical modification Nano silver grain can be obtained.
(formation of electrode)
As metal nanoparticle, containing the metallic nanoparticle period of the day from 11 p.m. to 1 a.m beyond Nano silver grain together with Nano silver grain, the dispersion of Nano silver grain manufactured using the method containing above-mentioned (a) is as the 1st dispersion, manufacture the dispersion of metal nanoparticle beyond Nano silver grain as the 2nd dispersion using the method containing above-mentioned (d), then mix the 1st dispersion of more than 75 weight % and less than the 2nd dispersion of 25 weight % so that the total content of the 1st and the 2nd dispersion reaches 100 weight %.It should be noted that, 1st dispersion is not limited to the dispersion of the Nano silver grain that the method containing above-mentioned (a) manufactures, it is possible to use the dispersion of the Nano silver grain that the dispersion of the Nano silver grain that the method containing above-mentioned (b) manufactures or the method containing above-mentioned (c) manufacture.
The method illustrating to use the dispersion (composition for electrode formation of solaode) of so manufacture below and form electrode.
First on base material, it is coated with engineering method by wet type and is coated with the above-mentioned dispersion of work (composition for electrode formation of solaode).The painting work that this wet type is coated with under engineering method makes the thickness after burning till be 0.1～2.0 μm, preferably 0.3～1.5 film forming in the range of μm.Above-mentioned base material can be any one in the substrate including silicon, glass, pottery, macromolecular material or metal containing transparent conductive material, or layered product of more than two kinds in silicon, glass, pottery, macromolecular material and metal containing transparent conductive material.Any one of the solar cell device of the preferred solar cell device of base material or band transparency electrode.Indium tin oxide (Indium Tin Oxide:ITO), antimony-doped tin oxide (Antimony Tin Oxide:ATO), nesa (stannum oxide SnO2), IZO (Indium Zic Oxide), AZO (aluminum doping ZnO) etc. can be listed as transparency electrode.The thin dielectric film of lead zirconate titanate (PZT) etc can also be formed at substrate surface.Can list as polymeric substrate, the substrate that polyimides or PET (polyethylene terephthalate) etc. are formed by organic polymer.Above-mentioned dispersion is applied to the surface of the transparency electrode of the surface of the opto-electronic conversion semiconductor layer of solar cell device or the solar cell device of band transparency electrode.
The thickness of the dispersion formed on base material is defined to the thickness after burning till and reaches in the range of 0.1～2.0 μm, the sheet resistance value of the electrode needed for being because less than solaode during 0.1 μm is inadequate, although do not have in characteristic during more than 2.0 μm is improper, but the usage amount of material is more than aequum, cause the waste of material.Above-mentioned wet type is coated with any one in the particularly preferred spraying process of engineering method, allotter rubbing method, spin-coating method, cutter coating, seam coating, ink-jet application method, silk screen print method, flexographic printing process or die coating method, but is not limited to this, available all of method.
Spraying process is to utilize compressed gas to make dispersion be vaporific to coat base material or pressurized dispersion body itself becomes the vaporific method coating base material, and allotter rubbing method for example is by putting into dispersion syringe and extrudes the piston of this syringe and the method that sprayed dispersion by the minute nozzle of syringe front end and coat base material.Spin-coating method is to drip dispersion on the base material rotated, utilize the method that the dispersion of this dropping is diffused to base material periphery by its centrifugal force, cutter coating is horizontal direction can to arrange the base material that the front end with cutter is separated with the gap of regulation movably, by supplying the method that dispersion downstream side moves horizontally base material on this cutter base material to the upstream side.Seam coating is the method making dispersion flow out from slit and being coated on base material, and ink-jet application method is filling dispersion, the method for ink jet printing on base material in the print cartridge of commercially available ink-jet printer.Silk screen print method is to use yarn to indicate material as pattern, the method transferring the dispersion to base material by the domain picture made thereon.Flexographic printing process is that the dispersion being stained with in version is not directly adherent to base material, and is transferred once to rubber sheet by version, rubber sheet be again transferred to the hydrophobic printing process utilizing ink of base material.Die coating method is the dispersion manifold supplied in mould distribution to be extruded on thin film by gap, the method being coated with the surface of the base material that industrial and commercial bank enters.Die coating method has gap coating method or slope flow coat mode for cloth, curtain coating.
Then, by the base material in film forming above in an atmosphere at a temperature of 130～400 DEG C, preferably 140～200 DEG C, keep 10 minutes～1 hour, preferably 15～40 minutes and burn till.At this; the firing temperature of the film of the dispersion formed on the thickness of the dispersion formed on base material or base material is defined to the scope of 130～400 DEG C; the sintering being because during less than 130 DEG C between metal nanoparticle is insufficient; it is difficult to desorbing or decomposition (segregated combustion) because of heat during protectant burning till simultaneously; organic detritus is remained in a large number in electrode after burning till; rotten or the aging electric conductivity of this residue and reflectance reduction; then cannot play the advantage in this production of low temperature process, i.e. manufacturing cost more than 400 DEG C and increase productivity reduction.The firing time of the film of the dispersion formed on base material is defined to 10 minutes～the scope of 1 hour; the sintering being because during less than 10 minutes between metal nanoparticle is insufficient; it is difficult to due to desorbing or decomposition (segregated combustion) by heat during protectant burning till simultaneously; organic detritus is remained in a large number in electrode after burning till; this residue is rotten or aging; the electric conductivity of electrode and reflectance reduction; if it exceeds characteristic is not then affected by 1 hour; but manufacturing cost increases and exceedes required cost, productivity reduces.
In the composition for electrode formation of above-mentioned solaode, a large amount of is 10～50nm containing primary particle size and the bigger metal nanoparticle of size, and therefore the specific surface area of metal nanoparticle reduces, and protective agent proportion diminishes.As a result, if using above-mentioned composition and forming the electrode of solaode, heat desorbing when the organic molecule in the most above-mentioned protective agent is owing to burning till or decomposition or eliminate and decompose, thus can obtain the electrode with silver as main constituent being substantially free of organic thing.Therefore, using, even if above-mentioned, the solaode being formed with above-mentioned electrode, Organic substance also undergoes no deterioration or aging, and the conductivity of electrode and reflectance can maintain high level, therefore can obtain the electrode of excellent in stability year in year out throughout the year.Specifically, even if above-mentioned electrode being contained in temperature be maintained at 100 DEG C and humidity was maintained at the constant temperature and humidity cabinet of 50% after 1000 hours, also the specific insulation of the electric conductivity of electrode, i.e. electrode can be maintained less than 2 × 10 by the electromagnetic wave more than 80% of the electromagnetic wave of electrode reflection wavelength 750～1500nm, i.e. visible region to infrared spectral range simultaneously-5Ω·cm(20×10-6Ω cm) this extremely low value.Using the solaode of so electrode of formation, high conductivity and high reflectance, year in year out excellent in stability can also be maintained even if using all the year round.
2nd embodiment
(compositions)
The composition for electrode formation of the solaode of the present invention, can be the composition as the compositions recorded with described 1st embodiment has, contain the compositions of one kind or two or more additive in metal-oxide, metal hydroxides, organo-metallic compound and silicone oil further.Owing to containing metal-oxide, metal hydroxides, organo-metallic compound or silicone oil as in additive compositions, be combined with the chemical of base material or anchoring effect increases or the wettability of metal nanoparticle under the firing process of 130～400 DEG C and base material is improved, thus lossless electric conductivity, the adaptation with base material can be improved.
If using said composition to form electrode, then can give the inhibition of the grain growth that the sintering between metal nanoparticle brings, therefore can form the electrode with good texture structure.The average surface roughness of the most controlled weaving structure structure.Using in the formation of electrode of the compositions of the present invention, be not necessarily to vacuum technology during due to film forming, the restriction of technique is little, it is also possible to the operating cost of manufacture equipment is greatly reduced.
If using the compositions without above-mentioned metal-oxide etc. and forming electrode, the surface roughness of the electrode then formed increases, it is generally understood that the concaveconvex shape of electrode surface has the condition of optimization photoelectric transformation efficiency, only surface roughness is big, it is impossible to form the electrode surface that photoelectric transformation efficiency is excellent.As the compositions of the present invention, by adjusting kind, the concentration etc. such as metal-oxide, the surface of optimized surface roughness can be formed.
The content of additive is 0.1～20%, preferably 0.2～10% of the weight of the Nano silver grain constituting metal nanoparticle.The content of additive less than 0.1%, then will not improve the adaptation of base material and electrode, if the content of additive is more than 20%, then the electric conductivity to the electrode formed has harmful effect, occurs specific insulation more than 2 × 10-5The adverse consequences of Ω cm.
As metal-oxide, the oxide containing at least one in aluminum, silicon, titanium, chromium, manganese, ferrum, cobalt, nickel, silver, copper, zinc, molybdenum, stannum, indium and antimony or composite oxides can be listed.Composite oxides specifically refer to, indium oxide-tin oxide system complex oxide (Indium Tin Oxide:ITO), stibium oxide-Sn system composite oxides (Antimony Tin Oxide:ATO), Indium sesquioxide .-Zinc oxide composite oxides (Indium Zinc Oxide:IZO) etc..As metal hydroxides, the hydroxide containing at least one in aluminum, silicon, titanium, chromium, manganese, ferrum, cobalt, nickel, silver, copper, zinc, molybdenum, stannum, indium and antimony can be listed.
As organo-metallic compound, the metallic soap of silicon, titanium, chromium, manganese, ferrum, cobalt, nickel, silver, copper, zinc, molybdenum, indium and stannum, metal complex or metal alkoxide can be listed.Such as, metallic soap can list nickel acetate, silver acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate etc..Metal complex can list, acetylacetone,2,4-pentanedione zinc complex, acetylacetone,2,4-pentanedione chromium complex, acetylacetone,2,4-pentanedione nickel complex etc..Metal alkoxide can list, butanol zirconium, isopropyl titanate, methyl silicate, isocyanatopropyl trimethoxy silane, TSL 8330 etc..Silicone oil can use both pure silicon oil and modified silicon oil.
Modified silicon oil can use a part at the side chain of polysiloxanes further to import organic group person (side chain type), import at two ends of polysiloxanes and import organic group person (single tip type) in organic group person (two tip type), any one in two ends of polysiloxanes and import organic group person (side chain two tip type) at the part of side chain and two ends of polysiloxanes.Modified silicon oil responding property silicone oil and non-reactive silicone oil, both can serve as the additive of the present invention and uses.It should be noted that, reactive silicone oil represents amino modified, epoxy-modified, carboxy-modified, carbinol-modified, sulfhydryl modified and xenogenesis functional group modification (epoxy radicals, amino, polyether-based), and non-reactive silicone oil represents polyether-modified, methyl styrene base is modified, alkyl-modified, higher fatty acids is ester modified, fluorine richness and hydrophilic special modification.
(forming method of compositions)
A () uses the situation of the Nano silver grain of the protective agent chemical modification by the organic molecule main chain that carbon number is 3 of carbon skeleton
First, as described 1st embodiment, modulation disperse medium is dispersed with the dispersion of metal (silver-colored) nanoparticle modified by the protection materials chemistry of the organic molecule main chain that carbon number is 3.Adjust the dispersion obtained, so that reaching in the range of 2.5～95 weight % relative to the final tenor (silver content) of dispersion 100 weight %.When disperse medium is containing alcohol solution, the water and the alcohols that adjust solvent the most respectively are more than 1% and more than 2%.
Then, this dispersion is made to contain the one kind or two or more additive in metal-oxide, metal hydroxides and organo-metallic compound further.Adjust the content of additive, so that reaching in the range of the 1/1000～1/5 of the weight of Nano silver grain.Thus; by the silver nanoparticle dispersion of the protective agent chemical modification of organic molecule main chain that the carbon number of carbon skeleton is 3 in disperse medium, the composition for electrode formation of the one kind or two or more additive contained further in metal-oxide, metal hydroxides and organo-metallic compound can be obtained.
When (b) uses by the Nano silver grain of protective agent chemical modification of the organic molecule main chain that carbon number is 2 of carbon skeleton, c () uses the situation of the Nano silver grain of the protective agent chemical modification by the organic molecule main chain that carbon number is 1 of carbon skeleton, d () uses the situation that carbon number is 3 of the carbon skeleton of protectant organic molecule main chain of the metal nanoparticle beyond chemical modification Nano silver grain, the situation that carbon number is 1 or 2 of the carbon skeleton of protectant organic molecule main chain of the metal nanoparticle beyond chemical modification Nano silver grain, also after being identically formed dispersion with embodiment 1, as above-mentioned (a), can contain selected from metal-oxide further, one kind or two or more additive in metal hydroxides and organo-metallic compound.Thus; it is scattered in disperse medium by the metal nanoparticle of the protective agent chemical modification of organic molecule main chain, the composition for electrode formation of the one kind or two or more additive contained further in metal-oxide, metal hydroxides and organo-metallic compound can be obtained.
As metal nanoparticle, in the case of containing the metal nanoparticle beyond Nano silver grain and Nano silver grain simultaneously, if the dispersion of the Nano silver grain to manufacture containing any of the above-described method is the 1st dispersion, is the 2nd dispersion with the dispersion of the metal nanoparticle beyond the Nano silver grain containing above-mentioned method manufacture, then mix the 1st dispersion of more than 75 weight % and less than the 2nd dispersion of 25 weight %, so that the total content of the 1st and the 2nd dispersion reaches 100 weight %.
(forming method of electrode)
The method illustrating to use the dispersion (composition for electrode formation of solaode) of so manufacture below and form electrode.
First on base material, it is coated with engineering method by wet type and is coated with the above-mentioned dispersion of work (composition for electrode formation of solaode).The painting work that this wet type is coated with under engineering method makes the thickness after burning till be 0.1～2.0 μm, preferably 0.3～1.5 film forming in the range of μm.Above-mentioned base material can be any one in the substrate comprising silicon, glass, pottery, macromolecular material or metal containing transparent conductive material, or layered product of more than two kinds in silicon, glass, pottery, macromolecular material and metal containing transparent conductive material.Any one of the solar cell device of the preferred solar cell device of base material or band transparency electrode.Can list as transparency electrode, ITO, ATO, nesa, IZO, AZO etc..The thin dielectric film of lead zirconate titanate (PZT) etc can also be formed at substrate surface.As polymeric substrate, the substrate utilizing the organic polymer such as polyimides or PET (polyethylene terephthalate) to be formed can be listed.Above-mentioned dispersion is applied to the surface of the transparency electrode of the solar cell device of the surface of opto-electronic conversion semiconductor layer of solar cell device, band transparency electrode.Above-mentioned wet type is coated with any one that engineering method is particularly preferably in spraying process, allotter rubbing method, spin-coating method, cutter coating, seam coating, ink-jet application method, silk screen print method, flexographic printing process or die coating method, but is not limited to this, can use any method.
Then, by the base material in film forming above, in an atmosphere or in the inert gas environment such as Chisso or argon, the temperature 130～400 DEG C, preferably 200～400 DEG C keeps 5 minutes～1 hour, preferably 15～40 minutes and burns till.
The thickness of the dispersion formed on base material is defined to the thickness after burning till and reaches to be defined in the range of 0.1～2.0 μm or by the firing temperature of the film of the dispersion formed on base material the scope of 130～400 DEG C, be in order at the reason as embodiment 1.The firing time of the film of the dispersion formed on base material is defined to 5 minutes～the scope of 1 hour; the sintering being because less than 5 minutes between then metal nanoparticle is insufficient; it is difficult to desorbing or decomposition (segregated combustion) because of heat during protectant burning till simultaneously; therefore organic detritus is remained in the electrode after burning till in a large number; the electric conductivity of the rotten or aging electrode of this residue and reflectance reduction; constantly characteristic is not affected although little more than 1; but manufacturing cost increases and exceedes required cost, productivity reduces.
In the composition for electrode formation of above-mentioned solaode, due to a large amount of metal nanoparticles bigger containing the size that primary particle size is 10～50nm, thus the specific surface area of metal nanoparticle reduces, and protective agent proportion diminishes.As a result, if using above-mentioned composition and forming the electrode of solaode, the heat when organic molecule in the most above-mentioned protective agent is difficult to owing to burning till and desorbing or decomposition or eliminate and decompose, the electrode with silver as main constituent being substantially free of organic thing can be obtained.Therefore, using, even if above-mentioned, the solaode being formed with above-mentioned electrode, Organic substance undergoes no deterioration or aging, and the conductivity of electrode and reflectance can maintain high level, therefore can obtain the electrode of excellent in stability year in year out throughout the year.Specifically, even if above-mentioned electrode being contained in temperature be maintained at 100 DEG C and humidity was maintained at the constant temperature and humidity cabinet of 50% after 1000 hours, the specific insulation of the electric conductivity of electrode, i.e. electrode can also be maintained less than 2 × 10 by the electromagnetic wave more than 80% of the electromagnetic wave of electrode reflection wavelength 750～1500nm, i.e. visible region to infrared spectral range simultaneously-5This extremely low value of Ω cm.
By burning till with above-mentioned condition, conductive coating can be formed on base material.The conductive coating formed can give the inhibition of the grain growth that the sintering between metal nanoparticle brings, thus has good texture structure.Due to kind and the addition of the additive in the compositions of use, the film of the average surface roughness controlling texture structure can be obtained.The conductive coating average surface roughness being preferably formed as is in the range of 10～100nm.If average surface roughness is within the above range, then reach the scope of the texture structure that the applicable backplate constituting base plate type solaode has.The conductive coating formed can obtain the ratio resistance of the ratio resistance itself having close to the metal constituting in compositions the metal nanoparticle contained, and also can obtain close to itself the excellent reflectance of reflectance of metal constituting the metal nanoparticle contained in compositions.
So, the forming method of the electrode of the present invention includes: is coated with engineering method with wet type on base material and is coated with the above-mentioned composition for electrode formation of work and the operation of film forming and the operation burnt till by the base material of the film forming above in the range of said temperature.In this forming method, on base material, wet type can be coated with work compositions and film forming, form electrode with the easy operation burnt till by the base material of film forming.So, being not necessarily to vacuum technology during due to film forming, the restriction of technique is little, it is also possible to the operating cost of manufacture equipment is greatly reduced.Using the solaode of so electrode of formation, high conductivity and high reflectance, year in year out excellent in stability can also be maintained even if using all the year round.
3rd embodiment
The forming method of the electrode of the solaode of the present invention, is coated with engineering method with wet type is coated with work composition for electrode formation and the operation of film forming and the forming method of operation burnt till by the base material of the film forming above for being included on base material.Specifically, for be included on base material with wet type be coated with engineering method be coated with work composition for electrode formation make the thickness after burning till be the film formation process in the range of 0.1～2.0 μm and by the base material of the film forming above in the forming method of 130～400 DEG C of operations burnt till.
The compositions used in the forming method of above-mentioned electrode can use the composition for electrode formation that described 1st embodiment or the 2nd embodiment are recorded.
The forming method of the electrode of the solaode of the invention described above, can be the composition including implementing base material the operation that primary coat processes.Base material is coated with work composition for electrode formation, burns till and before forming electrode, the primary coat that base material is implemented to carry out primary coat processes, thus can improve the adaptation of electrode and base material.Primary coat processes and carries out by being coated with following coating material on base material.Process the coating material used as primary coat, the coating material containing the one kind or two or more metal-oxide in Ag, Cu, Sn, Pd, Zn, Ni, Mo, Cr, Mn, Al, Zr, Ti, Ru, Pt, In and Si is preferable.As metal-oxide, Ag can be listed2O、CuO、PdO、ZnO、NiO、MoO2、Cr2O3、MnO2、Al2O3、ZrO、TiO2、In2O3、SiO2Deng.It addition, the coating material containing one kind or two or more resinae is preferable.Can list as resinae, acrylic acid, vinyl acetate, epoxy, polyester, polyurethane, cellulose, polyvinylpyrrolidone, they modified resin, containing them as the copolymer etc. of construction unit.Resinae is preferable using the one kind or two or more composition in isocyanate prepolymer composition, polyester component and polyether components as constituent, contains above-mentioned 3 compositions the most respectively as constituent.Isocyanate prepolymer composition can list 2,4 toluene diisocyanate, and polyester component can list polycaprolactone, and polyether components can list Polyethylene Glycol.Specifically, can list with 2,4 toluene diisocyanate, polycaprolactone and Polyethylene Glycol as constituent, its mol ratio is the copolymer of 20: 50: 1.Coating material containing one kind or two or more alkoxide is preferable.Metal alkoxide can list, tetraethoxysilane, four titanium butoxide, isopropyl titanate, butanol zirconium etc..Coating material containing one kind or two or more metallic soap is preferable.Metallic soap can list, calcium stearate, magnesium stearate, zinc stearate, 2 ethyl hexanoic acid stannum etc..Coating material containing one kind or two or more coupling agent is preferable.Coupling agent can list, 3-mercaptopropyi methyl dimethoxysilane, triethanol amine titanate etc..
(forming method of electrode)
Then, the method illustrating to use the dispersion (composition for electrode formation of solaode) with the method formation as the 1st embodiment or the 2nd embodiment and form electrode.
First, substrate surface is implemented primary coat to process.The coating process of coating material when base material enforcement primary coat is processed, particularly preferably any one in spraying process, allotter rubbing method, spin-coating method, cutter coating, seam coating, ink-jet application method, silk screen print method, flexographic printing process or die coating method, but it is not limited to this, it is possible to use any method.It is made to be dried 20～100 DEG C of holdings 10 seconds～30 minutes the coating material being coated with on base material.Or kept 10 seconds～30 minutes by the air-supplies of 20～100 DEG C and make its universe dry.Preferably keep within 15 seconds, keep by the air-supply of 40 DEG C and make its universe dry.Process as implementing primary coat, utilize composition for electrode formation to form the base material of electrode afterwards, can be any one of substrate including silicon, glass, pottery, macromolecular material or metal containing transparent conductive material, or layered product of more than two kinds in silicon, glass, pottery, macromolecular material and metal containing transparent conductive material.The base material containing at least one nesa coating or surface filming can also be used to have the base material of nesa coating.As nesa coating, Indium sesquioxide. system, Sn system, Zinc oxide can be listed.As Indium sesquioxide. system, Indium sesquioxide., ITO, IZO can be listed.As Sn system, nesa, ATO, fluorine-doped tin oxide can be listed.As Zinc oxide, zinc oxide, AZO, Ga-doped zinc oxide can be listed.In the solar cell device of the preferred solar cell device of base material or band transparency electrode any one.Transparency electrode can list ITO, ATO, nesa, IZO, AZO etc..Polymeric substrate can list the substrate utilizing the organic polymer such as polyimides or PET (polyethylene terephthalate) to be formed.The surface etc. on the surface of the opto-electronic conversion semiconductor layer of solar cell device or the transparency electrode of the solar cell device of band transparency electrode is implemented primary coat process.
Then, the composition for electrode formation (compositions that such as, embodiment 1 is recorded) being coated with engineering method painting work solaode on the base material that primary coat processes with wet type is being implemented.The painting work that this wet type is coated with under engineering method makes the thickness after burning till be 0.1～2.0 μm, preferably 0.3～1.5 film forming in the range of μm.Wet type is coated with any one in the particularly preferred spraying process of engineering method, allotter rubbing method, spin-coating method, cutter coating, seam coating, ink-jet application method, silk screen print method, flexographic printing process or die coating method, but is not limited to this, it is possible to use any method.
It follows that the base material of the film forming above is burnt till so that the temperature of 130～400 DEG C, preferably 140～300 DEG C keeps 10 minutes～1 hour, preferably 15～40 minutes in an atmosphere.At this, the thickness of the dispersion formed on base material is defined to the scope of 0.1～2.0 μm, the sheet resistance value of the electrode needed for being because less than solaode during 0.1 μm is inadequate, although if it exceeds 2.0 μm then do not have in characteristic improper, but the usage amount of material is more than aequum, cause the waste of material.The firing temperature of the film of the dispersion formed on base material is defined to the scope of 130～400 DEG C; the sintering being because during less than 130 DEG C between metal nanoparticle is insufficient; it is difficult to desorbing or decomposition (segregated combustion) due to heat during protectant burning till simultaneously; therefore organic detritus is remained in the electrode after burning till in a large number; rotten or the aging electric conductivity of this residue and reflectance reduction; the advantage in this production of low temperature process then can not be played more than 400 DEG C; i.e. manufacturing cost increases, and productivity reduces.The firing time of the film of the dispersion formed on base material is defined to 10 minutes～the scope of 1 hour; the sintering being because during less than 10 minutes between metal nanoparticle is insufficient; it is difficult to desorbing or decomposition (segregated combustion) because of heat during protectant burning till simultaneously; organic detritus is remained in a large number in electrode after burning till; the electric conductivity of the rotten or aging electrode of this residue and reflectance reduction; although characteristic will not be had harmful effect more than 1 hour; but manufacturing cost increases and exceedes required cost, productivity reduces.
In the composition for electrode formation of above-mentioned solaode, a large amount of metal nanoparticles bigger containing the size that primary particle size is 10～50nm, thus the specific surface area of metal nanoparticle reduces, protective agent proportion diminishes.As a result, if using above-mentioned composition and forming the electrode of solaode, the heat when organic molecule in the most above-mentioned protective agent is owing to burning till and desorbing or decomposition or eliminate and decompose, the electrode with silver as main constituent being substantially free of organic thing can be obtained.Therefore, even if use the above-mentioned solaode being formed with above-mentioned electrode throughout the year, Organic substance also undergoes no deterioration or aging, and the conductivity of electrode and reflectance can maintain high level, therefore can obtain the electrode of excellent in stability year in year out.Specifically, even if above-mentioned electrode being contained in temperature be maintained at 100 DEG C and humidity was maintained at the constant temperature and humidity cabinet of 50% after 1000 hours, the specific insulation of the electric conductivity of electrode, i.e. electrode can also be maintained less than 2 × 10 by the electromagnetic wave more than 80% of the electromagnetic wave of electrode reflection wavelength 750～1500nm, i.e. visible region to infrared spectral range simultaneously-5Ω·cm(20×10-6Ω cm) this extremely low value.Using the solaode of so electrode of formation, high conductivity and high reflectance, year in year out excellent in stability can also be maintained even if using all the year round.
[embodiment]
The following detailed description of examples and comparative examples of the present invention.
<embodiment A1>
First silver nitrate is dissolved in deionized water and modulates aqueous metal salt.On the other hand, in the sodium citrate aqueous solution of the concentration 26% sodium citrate being dissolved in deionized water and obtain, directly adding granular ferrous sulfate in the stream of nitrogen gas of temperature 35 DEG C and make it dissolve, modulation contains the reducing agent aqueous solution of citrate ions and ferrous ion with the mol ratio of 3: 2.Then, when above-mentioned stream of nitrogen gas being maintained at temperature 35 DEG C, making the stirrer of magnetic stirrer rotate with the rotary speed of 100rpm, stirring above-mentioned reducing agent aqueous solution, while dripping above-mentioned aqueous metal salt in this reducing agent aqueous solution and mixing.Here, adjust the concentration of each solution, so that the addition of aqueous metal salt reaches less than the 1/10 of the amount of reducing agent aqueous solution, even if thus dripping the aqueous metal salt of room temperature, reaction temperature is also held in 40 DEG C.Adjust the mixing ratio of above-mentioned two aqueous solutions, so that the equivalent of ferrous ion added as reducing agent reaches 3 times of the equivalent of metal ion.After the completion of dropwise addition of aqueous metal salt, the stirring of continuation mixed liquor 15 minutes, it is thus achieved that comprise the dispersion liquid of metallic colloid.The pH of this dispersion liquid is 5.5, and the stoichiometry growing amount of the metallic in dispersion liquid is 5g/ liter.Ambient temperatare puts the dispersion liquid of this acquisition, is separated the agglutinator of the metal nanoparticle of sedimentation by decant.
Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, continuation methanol replaces washing, and the content making metal (silver-colored) is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus be modulated to the Nano silver grain that primary particle size is 10～50nm that Nano silver grain contains average 71%, be i.e. adjusted under average relative to the primary particle size of all Nano silver grains 100% be the ratio shared by the Nano silver grain in the range of 10～50nm be 71%.With this dispersion for embodiment A1.It should be noted that and the mixed proportion of final metal (silver-colored), water, methanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 50.0 weight %, 2.5 weight %, 5.0 weight % and 42.5 weight % respectively.Here, solvent orange 2 A refers to mixed liquor acetone and Isopropanediol mixed with the ratio of weight ratio 1: 1.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.Although the protective agent of chemical modification Nano silver grain does not contains hydroxyl (-OH), but containing carbonyl (-C=O).It should be noted that ferrum in ferrous sulfate is removed when the replacement utilizing methanol is washed etc..
<embodiment A2>
Ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with ethanol, the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus being modulated to the Nano silver grain that primary particle size is 10～50nm that Nano silver grain contains average 72%, being i.e. adjusted under average relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% is 72%.With this dispersion for embodiment A2.It should be noted that and the mixed proportion of final metal (silver-colored), water, ethanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 50.0 weight %, 4.0 weight %, 5.0 weight % and 41.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.Although the protective agent of chemical modification Nano silver grain does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A3>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 73%, even if reaching 73% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average.With this dispersion for embodiment A3.It should be noted that and will be adjusted to 50.0 weight %, 1.0 weight %, 5.0 weight % and 44.0 weight % respectively relative to the final metal (silver-colored) of dispersion 100 weight %, water, the mixed proportion of second alcohol and solvent B.Here, solvent B refers to weight ratio 1: 1 hybrid ring hexane and the mixed liquor of butanone.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.Although the protective agent of chemical modification Nano silver grain does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A4>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 75%, even if reaching 75% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average.With this dispersion for embodiment A4.It should be noted that and the mixed proportion of final metal (silver-colored), water and ethanol relative to dispersion 100 weight % is adjusted to 50.0 weight %, 48.0 weight % and 2.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.Although the protective agent of chemical modification Nano silver grain does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A5>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 75%, even if reaching 75% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with gold chloride, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that golden nanometer particle contains the golden nanometer particle that particle diameter is 10～50nm of average 75%, even if reaching 75% relative to the ratio shared by the golden nanometer particle that primary particle size is 10～50nm of all golden nanometer particles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 95 weight % and the 2nd dispersion 5 weight %.With this dispersion for embodiment A5.It should be noted that and the mixed proportion of final metal (silver and the total of gold), water and ethanol relative to dispersion 100 weight % is adjusted to 50.0 weight %, 3.5 weight % and 46.5 weight % respectively.Nano silver grain in dispersion and golden nanometer particle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.Although the protective agent of chemical modification Nano silver grain and golden nanometer particle does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A6>
Centrifugal separator is utilized to be adjusted in the same manner as embodiment A2, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 71%, even if reaching 71% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with chloroplatinic acid, centrifugal separator is utilized to be adjusted in the same manner as embodiment A2, so that platinum nanoparticle contains the platinum nanoparticle that primary particle size is 10～50nm of average 75%, even if reaching 75% relative to the ratio shared by the platinum nanoparticle that primary particle size is 10～50nm of all platinum nanoparticles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 95 weight % and the 2nd dispersion 5 weight %.With this dispersion for embodiment A6.It should be noted that and the mixed proportion of final metal (silver and the total of platinum), water, ethanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 50.0 weight %, 3.5 weight %, 2.5 weight % and 44.0 weight % respectively.Nano silver grain in dispersion and platinum nanoparticle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and platinum nanoparticle contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A7>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with Palladous nitrate., centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Pd nano particle contains the Pd nano particle that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Pd nano particle that primary particle size is 10～50nm of all Pd nano particles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 77 weight % and the 2nd dispersion 23 weight %.With this dispersion for embodiment A7.
It should be noted that and the mixed proportion of final metal (silver and the total of palladium), water, ethanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 50.0 weight %, 1.5 weight %, 2.5 weight % and 46.0 weight % respectively.With the Nano silver grain in the protective agent of the organic molecule main chain that carbon skeleton is carbon number 3 respectively chemical modification dispersion and Pd nano particle.The protective agent of chemical modification Nano silver grain and Pd nano particle contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A8>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with ruthenium trichloride, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that ruthenium nano particle contains the ruthenium nano particle that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the ruthenium nano particle that primary particle size is 10～50nm of all ruthenium nano particles 100% under average, it is thus achieved that the 2nd dispersion.Then above-mentioned 1st dispersion 76 weight % and above-mentioned 2nd dispersion 24 weight % are mixed.With this dispersion for embodiment A8.It should be noted that and the mixed proportion of final metal (silver and the total of ruthenium), water, ethanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 75.0 weight %, 1.5 weight %, 2.0 weight % and 21.5 weight % respectively.Nano silver grain in dispersion and ruthenium nano particle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and ruthenium nano particle does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A9>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 73%, even if reaching 73% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with Nickel dichloride., centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that nickel nano particle contains the nickel nano particle that primary particle size is 10～50nm of average 73%, even if reaching 73% relative to the ratio shared by the nickel nano particle that primary particle size is 10～50nm of all nickel nano particles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 76 weight % and the 2nd dispersion 24 weight %.With this dispersion for embodiment A9.It should be noted that and the mixed proportion of final metal (silver and the total of nickel), water, ethanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 75.0 weight %, 2.2 weight %, 2.0 weight % and 20.8 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and nickel nano particle does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A10>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with cuprous nitrate, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that copper nano-particle contains the copper nano-particle that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the copper nano-particle that primary particle size is 10～50nm of all copper nano-particles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 76 weight % and the 2nd dispersion 24 weight %.With this dispersion for embodiment A10.It should be noted that and will be adjusted to 75.0 weight %, 4.0 weight %, 5.0 weight % and 16.0 weight % respectively relative to the final metal of dispersion 100 weight % (the silver-colored and total of copper), water, the mixed proportion of second alcohol and solvent B.Nano silver grain in dispersion and copper nano-particle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and copper nano-particle does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A11>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with stannum dichloride, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that sijna rice corpuscles contains the sijna rice corpuscles that particle diameter is 10～50nm of average 72%, i.e. reach 72% relative to the ratio shared by the sijna rice corpuscles that primary particle size is 10～50nm of all sijna rice corpuscles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 76 weight % and the 2nd dispersion 24 weight %.With this dispersion for embodiment A11.
It should be noted that and will be adjusted to 75.0 weight %, 4.0 weight %, 5.0 weight % and 16.0 weight % respectively relative to the final metal of dispersion 100 weight % (the silver-colored and total of stannum), water, the mixed proportion of second alcohol and solvent B.Nano silver grain in dispersion and sijna rice corpuscles are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and sijna rice corpuscles does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A12>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with indium nitrate, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that In nanoparticles contains the In nanoparticles that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the In nanoparticles that primary particle size is 10～50nm of all In nanoparticles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 80 weight % and the 2nd dispersion 20 weight %.With this dispersion for embodiment A12.
It should be noted that and the mixed proportion of final metal (silver and the total of indium), water, ethanol and solvent C relative to dispersion 100 weight % is adjusted to 75.0 weight %, 5.0 weight %, 5.0 weight % and 15.0 weight % respectively.Here, solvent C refers to the mixed liquor with weight ratio 1: 1 mixed toluene and hexane.Nano silver grain in dispersion and In nanoparticles are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and In nanoparticles does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A13>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 74%, even if reaching 74% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with zinc chloride, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that zinc nanoparticle contains the zinc nanoparticle that primary particle size is 10～50nm of average 74%, even if reaching 74% relative to the ratio shared by the zinc nanoparticle that primary particle size is 10～50nm of all zn nanoparticle 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 80 weight % and the 2nd dispersion 20 weight %.With this dispersion for embodiment A13.
It should be noted that and the mixed proportion of final metal (silver and the total of zinc), water and ethanol relative to dispersion 100 weight % is adjusted to 75.0 weight %, 10.0 weight % and 15.0 weight % respectively.Nano silver grain in dispersion and zinc nanoparticle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and zinc nanoparticle does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A14>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 75%, even if reaching 75% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with chromic sulfate, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that chromium nanoparticle contains the chromium nanoparticle that primary particle size is 10～50nm of average 75%, even if reaching 75% relative to the ratio shared by the chromium nanoparticle that primary particle size is 10～50nm of all chromium nanoparticles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 95 weight % and the 2nd dispersion 5 weight %.With this dispersion for embodiment A14.It should be noted that and the mixed proportion of final metal (silver and the total of chromium), water and ethanol relative to dispersion 100 weight % is adjusted to 75.0 weight %, 5.0 weight % and 20.0 weight % respectively.Nano silver grain in dispersion and chromium nanoparticle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and chromium nanoparticle does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A15>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with manganese sulfate, the dispersion replacing washing in the same manner as embodiment A2 with ethanol is adjusted with centrifugal separator, so that manganese nanoparticle contains the manganese nanoparticle that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the manganese nanoparticle that primary particle size is 10～50nm of all manganese nanoparticles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 95 weight % and the 2nd dispersion 5 weight %.With this dispersion for embodiment A15.It should be noted that and the mixed proportion of final metal (silver and the total of manganese), water and ethanol relative to dispersion 100 weight % is adjusted to 75.0 weight %, 3.0 weight % and 22.0 weight % respectively.Nano silver grain in dispersion and manganese nanoparticle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and manganese nanoparticle does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A16>
Ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then spent glycol and ethanol replace washing, and the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, it is modulated, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 71%, i.e. it is adjusted under average and reaches 71% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100%.With this dispersion for embodiment A16.It should be noted that and the mixed proportion of final metal (silver-colored), water, ethylene glycol and ethanol relative to dispersion 100% is adjusted to 35.0 weight %, 2.0 weight %, 1.0 weight % and 53.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain does not contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A17>
Ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with butanol, the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, it is modulated, so that the Nano silver grain Nano silver grain that particle diameter is 10～50nm that contains average 73%, being i.e. adjusted under average and reaching 73% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grain 100 weight %.With this dispersion for embodiment A17.It should be noted that and the mixed proportion of final metal (silver-colored), water, butanol and solvent orange 2 A relative to dispersion 100% is adjusted to 35.0 weight %, 1.5 weight %, 50.0 weight % and 13.5 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH), but does not contains carbonyl (-C=O).
<embodiment A18>
Ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with propylene glycol and ethanol, the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus it is modulated to the Nano silver grain that primary particle size is 10～50nm that Nano silver grain contains average 72%, is i.e. adjusted under average and reaches 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grain 100 weight %.With this dispersion for embodiment A18.It should be noted that and the mixed proportion of final metal (silver-colored), water, propylene glycol and ethanol relative to dispersion 100% is adjusted to 35.0 weight %, 2.0 weight %, 1.0 weight % and 62.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH), but does not contains carbonyl (-C=O).
<embodiment A19>
Using natrium malicum to replace in addition to sodium citrate when in the modulation of reducing agent aqueous solution, ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with diethylene glycol and ethanol, the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus being modulated to the Nano silver grain that primary particle size is 10～50nm that Nano silver grain contains average 72%, being i.e. adjusted under average relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% is 72%.With this dispersion for embodiment A19.
It should be noted that and the mixed proportion of final metal (silver-colored), water, diethylene glycol and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 5.0 weight %, 1.0 weight % and 59.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 2.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A20>
Using natrium malicum to replace in addition to sodium citrate when in the modulation of reducing agent aqueous solution, ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then spent glycol and ethanol replace washing, and the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus being modulated to the Nano silver grain that primary particle size is 10～50nm that Nano silver grain contains average 72%, being i.e. adjusted under average relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% is 72%.With this dispersion for embodiment A20.It should be noted that and the mixed proportion of final metal (silver-colored), water, glycerol and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 35.0 weight %, 1.0 weight % and 29.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 2.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A21>
Using sodium glycollate to replace in addition to sodium citrate when in the modulation of reducing agent aqueous solution, ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with diethylene glycol and ethanol, the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus it is modulated to the Nano silver grain that particle diameter is 10～50nm that Nano silver grain contains average 73%, is i.e. adjusted under average and reaches 73% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100%.With this dispersion for embodiment A21.It should be noted that and the mixed proportion of final metal (silver-colored), water and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 10.0 weight % and 55.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 1.Although the protective agent of chemical modification Nano silver grain does not contains hydroxyl (-OH), but containing carbonyl (-C=O).
<embodiment A22>
When the modulation of reducing agent aqueous solution, ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with erithritol and ethanol, the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus it is modulated to the Nano silver grain that particle diameter is 10～50nm that Nano silver grain contains average 73%, is i.e. adjusted under average and reaches 73% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100%.With this dispersion for embodiment A22.It should be noted that and will be adjusted to 35.0 weight %, 5.0 weight %, 1.0 weight %, 24.0 weight % and 35.0 weight % respectively relative to the final metal (silver-colored) of dispersion 100 weight %, water, erithritol, the mixed proportion of second alcohol and solvent B.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 2.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A23>
Using natrium malicum to replace in addition to sodium citrate when in the modulation of reducing agent aqueous solution, ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with isobornyl hexanol and ethanol, the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus it is modulated to the Nano silver grain that primary particle size is 10～50nm that Nano silver grain contains average 75%, is i.e. adjusted under average and reaches 75% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100%.With this dispersion for embodiment A23.It should be noted that and the mixed proportion of final metal (silver-colored), water, isobornyl hexanol and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 1.0 weight %, 1.0 weight % and 63.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 2.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A24>
Using natrium malicum to replace in addition to sodium citrate when in the modulation of reducing agent aqueous solution, ambient temperatare puts the dispersion liquid obtained as embodiment A1, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with methanol, the content making metal is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus it is modulated to the Nano silver grain that particle diameter is 10～50nm that Nano silver grain contains average 75%, is i.e. adjusted under average and reaches 75% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100%.With this dispersion for embodiment A24.
It should be noted that and the mixed proportion of final metal (silver-colored), water and methanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 30.0 weight % and 35.0 weight % respectively.Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 2.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A25>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 71%, even if reaching 71% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with Nickel dichloride., centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that nickel nano particle contains the nickel nano particle that primary particle size is 10～50nm of average 71%, even if reaching 71% relative to the ratio shared by the nickel nano particle that primary particle size is 10～50nm of all nickel nano particles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 98 weight % and the 2nd dispersion 2 weight %.With this dispersion for embodiment A25.It should be noted that and the mixed proportion of final metal (silver and the total of nickel), water and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 5.0 weight % and 60.0 weight % respectively.Nano silver grain in dispersion and nickel nano particle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and nickel nano particle contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A26>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 71%, even if reaching 71% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with cuprous nitrate, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that copper nano-particle contains the copper nano-particle that particle diameter is 10～50nm of average 71%, even if reaching 71% relative to the ratio shared by the copper nano-particle that primary particle size is 10～50nm of all copper nano-particles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 98 weight % and the 2nd dispersion 2 weight %.With this dispersion for embodiment A26.It should be noted that and the mixed proportion of final metal (silver and the total of copper), water and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 5.0 weight % and 60.0 weight % respectively.Nano silver grain in dispersion and copper nano-particle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and copper nano-particle contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A27>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with stannum dichloride, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that sijna rice corpuscles contains the sijna rice corpuscles that particle diameter is 10～50nm of average 72%, even if reaching 72 weight % relative to the ratio shared by the sijna rice corpuscles that primary particle size is 10～50nm of all sijna rice corpuscles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 98 weight % and the 2nd dispersion 2 weight %.With this dispersion for embodiment A27.It should be noted that and the mixed proportion of final metal (silver and the total of stannum), water and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 2.0 weight % and 63.0 weight % respectively.Nano silver grain in dispersion and sijna rice corpuscles are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and sijna rice corpuscles contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A28>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with zinc chloride, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that zinc nanoparticle contains the zinc nanoparticle that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the zinc nanoparticle that primary particle size is 10～50nm of all zn nanoparticle 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 98 weight % and the 2nd dispersion 2 weight %.With this dispersion for embodiment A28.It should be noted that and the mixed proportion of final metal (silver and the total of zinc), water and methanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 2.0 weight % and 63.0 weight % respectively.Nano silver grain in dispersion and zinc nanoparticle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and zinc nanoparticle contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A29>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with chromic sulfate, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that chromium nanoparticle contains the chromium nanoparticle that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the chromium nanoparticle that primary particle size is 10～50nm of all chromium nanoparticles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 99 weight % and the 2nd dispersion 1 weight %.With this dispersion for embodiment A29.
It should be noted that and the mixed proportion of final metal (silver and the total of chromium), water and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 2.0 weight % and 63.0 weight % respectively.Nano silver grain in dispersion and chromium nanoparticle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and chromium nanoparticle contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A30>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, it is thus achieved that the 1st dispersion.On the other hand, the silver nitrate of embodiment A2 is replaced with manganese sulfate, centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A2 with ethanol, so that manganese nanoparticle contains the manganese nanoparticle that primary particle size is 10～50nm of average 72%, even if reaching 72% relative to the ratio shared by the manganese nanoparticle that primary particle size is 10～50nm of all manganese nanoparticles 100% under average, it is thus achieved that the 2nd dispersion.Then mixing the 1st dispersion 99 weight % and the 2nd dispersion 1 weight %.With this dispersion for embodiment A30.It should be noted that and the mixed proportion of final metal (silver and the total of manganese), water and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 2.0 weight % and 63.0 weight % respectively.Nano silver grain in dispersion and manganese nanoparticle are respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain and manganese nanoparticle contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A31>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A1 with methanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 100%, even if reaching 100% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, obtain dispersion.With this dispersion for embodiment A31.It should be noted that and the mixed proportion of final metal (silver-colored), water and methanol relative to dispersion 100 weight % is adjusted to 3.5 weight %, 1.0 weight % and 95.5 weight % respectively.Nano silver grain in dispersion is respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH) and carbonyl (-C=O).
<embodiment A32>
Centrifugal separator is utilized to adjust the dispersion replacing washing in the same manner as embodiment A1 with methanol, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 100%, even if reaching 100% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average, obtain dispersion.With this dispersion for embodiment A32.It should be noted that and the mixed proportion of final metal (silver-colored), water and methanol relative to dispersion 100 weight % is adjusted to 90.0 weight %, 9.8 weight % and 0.2 weight % respectively.Nano silver grain in dispersion is respectively by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.The protective agent of chemical modification Nano silver grain contains hydroxyl (-OH) and carbonyl (-C=O).
<Comparative examples A 1>
Centrifugal separator adjustment methanol is utilized to replace the dispersion of washing, so that Nano silver grain contains the Nano silver grain that primary particle size is 10～50nm of average 68%, even if reaching 68% relative to the ratio shared by the Nano silver grain that primary particle size is 10～50nm of all Nano silver grains 100% under average.The mixed proportion of final metal (silver-colored), water and methanol relative to dispersion 100 weight % is adjusted to 50.0 weight %, 2.5 weight % and 47.5 weight % respectively.Than that described above, dispersion is modulated in the same manner as embodiment A1.With this dispersion for Comparative examples A 1.
<Comparative examples A 2>
Mevalonic acid sodium is used to replace sodium citrate during the modulation of reducing agent aqueous solution, the mixed proportion of final metal (silver-colored), water and ethanol relative to dispersion 100 weight % is adjusted to 50.0 weight %, 4.0 weight % and 46.0 weight % respectively, in addition modulates dispersion in the same manner as embodiment A2.With this dispersion for Comparative examples A 2.It should be noted that Nano silver grain in dispersion is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 4.
<Comparative examples A 3>
The mixed proportion of final metal (silver-colored), water, ethanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 50.0 weight %, 0.7 weight %, 30.0 weight % and 19.3 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A3.With this dispersion for Comparative examples A 3.
<Comparative examples A 4>
50.0 weight %, 40.0 weight %, 1.0 weight % and 9.0 weight % will be adjusted to respectively relative to the final metal (silver-colored) of dispersion 100 weight %, water, the mixed proportion of second alcohol and solvent B, in addition, dispersion is modulated in the same manner as embodiment A4.With this dispersion for Comparative examples A 4.
<Comparative examples A 5>
Washing is replaced with propanol, mix the 1st dispersion 73 weight % and the 2nd dispersion 27 weight %, the mixed proportion of final metal (silver and gold), water, propanol and solvent C relative to dispersion 100 weight % is adjusted to 50.0 weight %, 3.5 weight %, 30.0 weight % and 16.5 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A5.With this dispersion for Comparative examples A 5.
<Comparative examples A 6>
Mix the 1st dispersion 74 weight % and the 2nd dispersion 26 weight %, the mixed proportion of final metal (silver and platinum), water and ethanol relative to dispersion 100 weight % is adjusted to 75.0 weight %, 3.5 weight % and 21.5 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A6.With this dispersion for Comparative examples A 6.
<Comparative examples A 7>
Mix the 1st dispersion 73 weight % and the 2nd dispersion 27 weight %, the mixed proportion of final metal (silver and palladium), water and ethanol relative to dispersion 100 weight % is adjusted to 75.0 weight %, 2.2 weight % and 22.8 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A7.With this dispersion for Comparative examples A 7.
<Comparative examples A 8>
Mix the 1st dispersion 74 weight % and the 2nd dispersion 26 weight %, the mixed proportion of final metal (silver and ruthenium), ethanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 75.0 weight %, 15.0 weight % and 10.0 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A8.With this dispersion for Comparative examples A 8.
<Comparative examples A 9>
Mix the 1st dispersion 74 weight % and the 2nd dispersion 26 weight %, 75.0 weight %, 2.2 weight %, 12.8 weight % and 10.0 weight % will be adjusted to respectively relative to the final metal of dispersion 100 weight % (silver-colored and nickel), water, the mixed proportion of second alcohol and solvent B, in addition, dispersion is modulated in the same manner as embodiment A9.With this dispersion for Comparative examples A 9.
<Comparative examples A 10>
Mix the 1st dispersion 72 weight % and the 2nd dispersion 28 weight %, the mixed proportion of final metal (silver and copper), water, ethanol and solvent C relative to dispersion 100 weight % is adjusted to 75.0 weight %, 4.0 weight %, 11.0 weight % and 10.0 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A10.With this dispersion for Comparative examples A 10.
<Comparative examples A 11>
Mix the 1st dispersion 73 weight % and the 2nd dispersion 27 weight %, the mixed proportion of final metal (silver and stannum), water and methanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 4.0 weight % and 61.0 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A11.With this dispersion for Comparative examples A 11.
<Comparative examples A 12>
Mix the 1st dispersion 74 weight % and the 2nd dispersion 26 weight %, the mixed proportion of final metal (silver and indium), water and ethanol relative to dispersion 100 weight % is adjusted to 35.0 weight %, 30.0 weight % and 35.0 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A12.With this dispersion for Comparative examples A 12.
<Comparative examples A 13>
Mix the 1st dispersion 74 weight % and the 2nd dispersion 26 weight %, the mixed proportion of final metal (silver and zinc), water, ethanol and solvent orange 2 A relative to dispersion 100 weight % is adjusted to 35.0 weight %, 10.0 weight %, 20.0 weight % and 35.0 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A13.With this dispersion for Comparative examples A 13.
<Comparative examples A 14>
Mix the 1st dispersion 73 weight % and the 2nd dispersion 27 weight %, 35.0 weight %, 5.0 weight %, 20.0 weight % and 40.0 weight % will be adjusted to respectively relative to the final metal of dispersion 100 weight % (silver-colored and chromium), water, the mixed proportion of second alcohol and solvent B, in addition, dispersion is modulated in the same manner as embodiment A14.With this dispersion for Comparative examples A 14.
<Comparative examples A 15>
Mix the 1st dispersion 74 weight % and the 2nd dispersion 26 weight %, the mixed proportion of final metal (silver and manganese), water, ethanol and solvent C relative to dispersion 100 weight % is adjusted to 35.0 weight %, 3.0 weight %, 20.0 weight % and 42.0 weight % respectively, in addition, dispersion is modulated in the same manner as embodiment A15.With this dispersion for Comparative examples A 15.
<comparative test 1 and evaluation>
Coating Examples A1～A32 and the dispersion of Comparative examples A 1～A15 on base material, so that after the thickness after burning till is the thickness shown in table 3 below and table 4, burning till with the temperature shown in table 3 below and table 4, thus form electrode on base material.The solaode of band ito film is used, without ito film solaode, silicon substrate, glass plate, polyimide plate, PET film or the glass plate of band ito film as base material.For being formed with the base material of these electrodes, before carrying out atmospheric exposure test, measure reflectance and the electric conductivity of the electrode formed on each base material, simultaneously after carrying out atmospheric exposure test, measure reflectance and the electric conductivity of the electrode formed on each base material.The results are shown in table 3 and table 4.
It should be noted that atmospheric exposure test is contained in temperature and is maintained at 100 DEG C of humidity by will be formed with the base material of electrode and is maintained at the constant temperature and humidity cabinet 1000 hours of 50% and carries out.
Electromagnetic wave (infrared ray and visible ray) to electrode illumination wavelength 750～1500nm, use ultraviolet-uisible spectrophotometer (V-570: light splitting society of Japan system) to measure the electromagnetic wave of reflection, calculate the ratio (%) of the volume reflection relative to total irradiation dose and obtain reflectance.
The primary particle size of metal nanoparticle uses FE-TEM (field emission type transmission electron microscope: NEC society system) to measure, and primary particle size is that the ratio shared by the Nano silver grain of 10～50nm is evaluated by image procossing measurement particle diameter number by the photo of the primary particle size of the metal nanoparticle using above-mentioned FE-TEM to shoot.
Electric conductivity is tried to achieve as the specific insulation (Ω cm) being measured by four-terminal method and calculating.Specifically, first the thickness to the electrode after burning till uses SEM (ultramicroscope S800: society of Hitachi system) directly to be measured the thickness of electrode by electrode sections, then use the ratio resistance measurer (ロ レ ス タ: society of Mitsubishi Chemical system) utilizing four-terminal method, this determinator inputs the thickness of the electrode of above-mentioned actual measurement and measures the specific insulation of electrode.
For hydroxyl (-OH), the presence or absence of carbonyl (-C=O), combination uses XPS (the x-ray photoelectron analytical equipment of Quantum2000:PHI society), TOF-SIMS the time-of-flight type secondary ion mass spectrometry device of society (TOF-SIMS IV:ION-TOF), the equipment analysis of FTIR (the fourier-transform infrared spectrophotometer of NEXUS670:Nicolet society) and TPD-MS (the intensification thermal desorption quality analysis apparatus of 5973N:Agilent society) to confirm existence.
On the other hand, the ratio shared by the metal nanoparticle that primary particle size is 10～50nm in the dispersion of embodiment A1 shown in Tables 1 and 2～A32 and Comparative examples A 1～A15, the carbon number of organic molecule main chain, the presence or absence of hydroxyl (-OH), the presence or absence of carbonyl (-C=O), the kind of dispersion (compositions) and mixed proportion, the kind of dissimilar metal (metal beyond silver) and containing ratio (with the containing ratio of dissimilar metal when adding up to 100 weight % of the metal beyond silver and silver).Reflectance shown in table 3 and table 4, electric conductivity (specific insulation) and weatherability, and the kind of base material, thickness and firing temperature.In weatherability one hurdle of table 3 and table 4, " well " represents that reflectance is more than 80% and specific insulation is less than 20 × 10-6The situation of Ω cm, less than 80% and specific insulation is less than 20 × 10 for " bad " expression reflectance-6Ω cm or reflectance are more than 80% and specific insulation is more than 20 × 10-6Ω cm or reflectance less than 80% less than and specific insulation more than 20 × 10-6The situation of Ω cm.
It should be noted that, in alcohols one hurdle of Tables 1 and 2, " ME " represents methanol, and " ET " represents ethanol, " EG " represents ethylene glycol, " BU " represents butanol, and " PG " represents propylene glycol, and " DEG " represents diethylene glycol, " GL " represents glycerose, " ER " represents erithritol, and " IH " represents isobornyl hexanol, and " PR " represents propanol.
In other solvent one hurdles of Tables 1 and 2, " A " represents with weight ratio 1: 1 mixing acetone and the mixed liquor of Isopropanediol, " B " represents that, with weight ratio 1: 1 hybrid ring hexane and the mixed liquor of butanone, " C " represents with weight ratio 1: 1 mixed toluene and the mixed liquor of hexane.
[table 1]
[table 2]
[table 3]
[table 4]
From in table 3 and table 4, Comparative examples A 1 and Comparative examples A 3, after just having burnt till, i.e. the reflectance of electrode before atmospheric exposure test has been more than 80% and specific insulation is less than 20 × 10-6Ω cm, initial stage characteristic is highly satisfactory, but after carrying out atmospheric exposure test, the reflectance of electrode and specific insulation reduce (deterioration with age), become bad.In other comparative examples, either one or both in the reflectance of the electrode before atmospheric exposure test or specific insulation is not enough, and the reflectance of the electrode after atmospheric exposure test and specific insulation also become bad.On the other hand, in embodiment, no matter before atmospheric exposure test or after atmospheric exposure test, the reflectance of electrode be more than 80% and specific insulation less than 20 × 10-6Ω cm, initial stage characteristic and weatherability before atmospheric exposure test are the most highly satisfactory.
<embodiment B1～B32>
First, silver nitrate is dissolved in deionized water modulation aqueous metal salt.On the other hand, in the sodium citrate aqueous solution of the concentration 26% sodium citrate being dissolved in deionized water and obtain, being directly added into granular ferrous sulfate in the stream of nitrogen gas of temperature 35 DEG C and make it dissolve, modulation contains the reducing agent aqueous solution of citrate ions and ferrous ion with the mol ratio of 3: 2.Then when above-mentioned stream of nitrogen gas being maintained at temperature 35 DEG C, with the stirrer of 100rpm rotary speed rotation magnetic force blender, above-mentioned reducing agent aqueous solution is stirred, while dripping above-mentioned aqueous metal salt in this reducing agent aqueous solution and mixing.Here, adjust each solution concentration so that aqueous metal salt the amount that addition is reducing agent aqueous solution less than 1/10, even if thus drip room temperature aqueous metal salt, reaction temperature is also maintained at 40 DEG C.
Adjust the mixing ratio of above-mentioned two aqueous solutions, so that the equivalent of ferrous ion added as reducing agent reaches 3 times of the equivalent of metal ion.After the completion of dropwise addition of aqueous metal salt, the stirring of continuation mixed liquor 15 minutes, obtain comprising the dispersion liquid of metallic colloid.The pH of this dispersion liquid is 5.5, and the stoichiometry growing amount of the metallic in dispersion liquid is 5g/ liter.Ambient temperatare puts the dispersion liquid of this acquisition, utilizes decant to separate the agglutinator of the metal nanoparticle that Shen drops.
Adding deionized water in this separator and make dispersion, after carrying out desalting processing by sucking filtration, then replace washing with methanol, the content making metal (silver-colored) is 50 weight %.Afterwards, centrifugal separator is used to adjust the centrifugal force of this centrifugal separator and separating coarse-grained son, thus be modulated to the Nano silver grain that primary particle size is 10～50nm that Nano silver grain contains average 71%, be i.e. adjusted under average relative to the primary particle size of all Nano silver grains 100% be the ratio shared by the Nano silver grain in the range of 10～50nm be 71%.The Nano silver grain obtained is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.
Then, Nano silver grain 10 weight portion so adjusted is scattered in the mixed solution containing water, ethanol and methanol.By adding additive 1 weight portion shown in table 5 below, table 6 in dispersion liquid, it is thus achieved that composition for electrode formation.Then the compositions spin coater of acquisition is coated on the base material shown in table 5 below, table 6 so that after thickness after burning till is 300nm, burning till at 200 DEG C 20 minutes, thus forming electrode on base material.It should be noted that in additive, metal-oxide and metal hydroxides add in the way of having the water of mean diameter of 1～100nm, ethanol mixed stocker colloid.
<comparative example B1～B5>
Nano silver grain 10 weight portion making the mean diameter about 20nm by the method adjustment as embodiment B1～B32 is scattered in the mixed solution containing water, ethanol and methanol.This dispersion liquid is added without additive as composition for electrode formation.The compositions spin coater of acquisition is coated on the base material shown in table 6 below so that after thickness after burning till is 300nm, burning till at 200 DEG C 20 minutes, thus forming electrode on base material.
<comparative test 2>
For being formed with in embodiment B1～B32 and comparative example B1～B5 the base material of the electrode obtained, evaluate electric conductivity and the cementability to base material.Electric conductivity is obtained as the specific insulation (Ω cm) utilizing four-terminal method to measure and calculating.Specifically, first the thickness to the electrode after burning till uses SEM (ultramicroscope of society of Hitachi: S800) directly to be measured the thickness of electrode by electrode sections, then use the ratio resistance measurer (Mitsubishi Chemical ロ レ ス タ GP) utilizing four-terminal method, this determinator inputs the thickness of the electrode of above-mentioned actual measurement and measures the specific insulation of electrode.The adaptation of base material is evaluated qualitatively by the adhesive tape of the base material forming electrode tears stripping test, " well " represents situation about peeling off from base material only adhesive tape, " neutral " represents the stripping of adhesive tape and exposes the situation that the state of substrate surface is mixed in, and " bad " represents the situation that substrate surface exposes comprehensively owing to adhesive tape tears stripping.The results are shown in table 5 and table 6.
[table 5]
[table 6]
From table 5 and table 6, using and do not contain metal-oxide, metal hydroxides or organo-metallic compound as in comparative example B1～B5 of the compositions of additive, conductivity represents 10-6The numerical value of rank, cementability evaluation all shows " bad " in all of example, and the electrode of formation is peeled off by adhesive tape, and substrate surface exposes.On the other hand, in embodiment B1～B32, there is the electric conductivity of excellence, cementability evaluation displays that " well " or " neutral ", by adding the one kind or two or more additive in metal-oxide, metal hydroxides and organo-metallic compound in composition for electrode formation, can confirm that lossless electric conductivity, the adaptation with base material can be improved.
<embodiment B33～B57 and comparative example B6, B7>
First, the dissolving metal salts of the kind of the metal nanoparticle shown in table 7 below and table 8 will be formed in deionized water, modulation aqueous metal salt.Sodium citrate is dissolved in deionized water and modulates the sodium citrate aqueous solution that concentration is 26 weight %.Being directly added into granular ferrous sulfate to this sodium citrate aqueous solution in being maintained at the stream of nitrogen gas of 35 DEG C and make it dissolve, modulation contains the reducing agent aqueous solution of citrate ions and ferrous ion with the mol ratio of 3: 2.
Then, when above-mentioned stream of nitrogen gas is maintained at 35 DEG C, the stirrer of magnetic stirrer is put in reducing agent aqueous solution, stirrer is made to rotate with the rotary speed of 100rpm, while stirring above-mentioned reducing agent aqueous solution, in this reducing agent aqueous solution, dripping above-mentioned aqueous metal salt and mix.Here, adjust the concentration of each solution, so that the addition of the aqueous metal salt in reducing agent aqueous solution reaches less than the 1/10 of the amount of reducing agent aqueous solution, even if thus the aqueous metal salt reaction temperature of dropping room temperature is also maintained at 40 DEG C.Adjust above-mentioned reducing agent aqueous solution and the mixing ratio of aqueous metal salt, so that the equivalent of ferrous ion added as reducing agent reaches 3 times of the equivalent of metal ion.After reducing agent aqueous solution dropping aqueous metal salt terminates, continue the stirring of 15 minutes mixed liquors, thus make mixed liquor internal generation metallic, it is thus achieved that be dispersed with the metallic dispersion liquid of metallic.The pH of metallic dispersion liquid is 5.5, and the stoichiometry growing amount of the metallic in dispersion liquid is 5g/ liter.
Put the dispersion liquid of acquisition by ambient temperatare, make the metallic Shen in dispersion liquid drop, separated the agglutinator of the metallic of Shen fall by decant.Adding deionized water in the metal agglutinator separated and make dispersion, utilize sucking filtration to carry out desalting processing time, again with methanol replaces washing, and the content making metal is 50 weight %.Afterwards, using centrifugal separator to adjust the centrifugal force of this centrifugal separator, by the particle separation diameter bigger metallic more than 100nm, being adjusted to the primary particle size containing average 71% is the metal nanoparticle in the range of 10～50nm.That is, being adjusted under average relative to the primary particle size of all metal nanoparticles 100% is that the ratio shared by the metal nanoparticle in the range of 10～50nm reaches 71%.The metal nanoparticle obtained is by the protective agent chemical modification of organic molecule main chain that carbon skeleton is carbon number 3.
Then, metal nanoparticle 10 weight portion of acquisition is added and is mixed in mixed solution 90 weight portion containing water, ethanol and methanol and makes it disperse, in this dispersion liquid, add the additive shown in table 7 below and table 8 according still further to the ratio shown in table 7 and table 8, obtain embodiment B33～the coated test compositions of B57 and comparative example B6, B7 respectively.It should be noted that the Nano silver grain that the metal nanoparticle of the coated test compositions constituting embodiment B33～B57 contains more than 75 weight %.
<comparative test 3>
The coated test compositions obtained in embodiment B33～57 and comparative example B6, B7 is coated on the base material shown in table 7 below and table 8 so that the thickness after burning till is for 10 with various film build methods2～2 × 103After nm, burn till with the heat treatment condition shown in table 7 below and table 8, on base material, thus form conductive coating.
For the conductive coating formed, obtain electric conductivity, reflectance, coating thickness and average surface roughness respectively.Electrical conductivity evaluations is carried out in the same manner as above-mentioned comparative test 2.The reflectance evaluation of film utilizes the combination of ultraviolet-uisible spectrophotometer and integrating sphere, the scattered reflection rate of the film under mensuration wavelength 800nm.Coating thickness measures by utilizing the cross-section of SEM.By evaluating atomic force microscope (Atomic Force Microscope according to JIS B0601；AFM) evaluation of estimate that the surface configuration obtained relates to, obtains average surface roughness.Its result is shown in Table 9 and table 10 respectively.
[table 7]
[table 8]
[table 9]
[table 10]
From table 9 and table 10, the conductive coating that the conductive coating using the compositions of embodiment B33～B57 to be formed and the compositions using comparative example B6 are formed is compared, it is equal to than resistance and reflectance, but the average surface roughness for film, comparative example B6 is 110nm, and embodiment B33～B57 are in the range of 10～100nm, can confirm that the surface roughness of the scope obtaining the texture structure that the backplate being suitable for constituting base plate type solaode has.It addition, use in the conductive coating that the compositions of comparative example B7 is formed, it is known that the ratio of the Nano silver grain that metal nanoparticle contains is if less than 5 weight %, then specific insulation rises, the reflectance reduction under 800nm.
<embodiment B58, B59 and comparative example B8, B9>
The coated test compositions used in embodiment B34 is coated on the base material shown in following table B6 so that after thickness after burning till is respectively 100nm (embodiment B58), 500nm (embodiment B59), 50nm (comparative example B8) and 70nm (comparative example B9) with various film build methods, burn till with the heat treatment condition shown in table 11 below, on base material, thus form conductive coating.
For the conductive coating formed, obtain respectively than resistance, reflectance, coating thickness and average surface roughness in the same manner as above-mentioned comparative test 3.Its result is shown in table 12.
[table 11]
[table 12]
As table 12 understands, for the film manufactured with identical conditions in addition to thickness, compared with thickness comparative example B8 and B9 less than 100nm, if as embodiment B58 thickness the same with B59 is more than 100nm, then reflectance is more than 90%, is 4 × 10 than resistance6Ω cm value below, shows the most certain value.It is thought that because thickness less than 100nm time, by sintering cannot form continuous film, the some of incident illumination through film cause reflectance reduce or interparticle contact point deficiency cause the increase than resistance.
<embodiment B60, B61 and comparative example B10, B11>
Metal nanoparticle 10 weight portion shown in table 13 below is added and is mixed in mixed solution 90 weight portion containing water, ethanol and methanol and makes it disperse, in this dispersion liquid, adds methyl silicate as additive according still further in compositions containing the ratio of 1 weight %, acquisition embodiment B60, B61 and the coated test compositions of comparative example B10, B11 the most respectively.
<comparative test 4>
The coated test compositions obtained in embodiment B60, B61 and comparative example B10, B11 is coated on glass substrate with allotter coating process to reach 102～2 × 103After the thickness of nm, under atmospheric environment, burn till at 320 DEG C 20 minutes, on base material, thus form conductive coating.
For the conductive coating formed, obtain electric conductivity, reflectance and cementability evaluation respectively.Electric conductivity and cementability evaluation are carried out in the same manner as above-mentioned comparative test 2, and reflectance evaluation is carried out in the same manner as above-mentioned comparative test 3.Its result is shown in table 14.
[table 13]
[table 14]
As table 14 understands, if the carbon number of the carbon skeleton of the organic molecule of chemical modification Nano silver grain is more than 3, then specific insulation rises, the reflectance reduction under 800nm.It addition, if the Nano silver grain proportion that mean diameter is 10～50nm is less than average 70%, then specific insulation rises, the reflectance reduction under 800nm.
<embodiment C1～C35>
Prepare to be scattered in metal nanoparticle 10 weight portion of table 15 below, table 16 and the mean diameter about 20nm shown in table 17 composition for electrode formation of the mixed solution of water, ethanol and methanol.
It should be noted that, the composition for electrode formation used in embodiment C1～C35 only uses the nano grain of silver period of the day from 11 p.m. to 1 a.m, the containing ratio of the Nano silver grain in metal nanoparticle is 100%, when using both the metal nanoparticles beyond Nano silver grain and silver, the containing ratio of the Nano silver grain in metal nanoparticle is 95%.It addition, the carbon skeleton of the organic molecule of chemical modification metal nanoparticle is carbon number 3, the primary particle size contained by metal nanoparticle be the average of the metal nanoparticle in the range of 10～50nm be 80%.Additionally prepare table 15, table 16 and the primary coat coating material of the mixed solution being scattered in water, ethanol and methanol containing material 1 weight portion shown in table 17.
Prepare table 15, table 16 and the base material shown in table 17.Then, by the coating process coating primary coat coating material shown in table 15 below, table 16 and table 17 on base material, 60 DEG C, 30 minutes it are dried in an atmosphere.Then, carrying out on the base material of coating of this primary coat coating material by table 15 below, table 16 and the coating process film forming composition for electrode formation shown in table 17 so that after thickness after burning till reaches 300nm, burn till 30 minutes at a temperature of table 15, table 16 and table 17 are shown and burn till, base material is formed electrode.It should be noted that in table 15 below, in table 16 and the spray C shown in table 17 represents that spraying, distributor C represent that allotter is coated with, ink-jet C represents that ink-jet application, rotation C represent that spin coating, mould C represent that die coating, cutter C represent that cutter is coated with, and seam C represents seam painting.Pet sheet in table 16, table 17 shows polyethylene terephthalate.
<comparative example C1～C5>
Prepare to be scattered in metal nanoparticle 10 weight portion of the about 20nm of the mean diameter shown in table 17 below the composition for electrode formation of the mixed solution of water, ethanol and methanol.The containing ratio of the Nano silver grain that it should be noted that in comparative example C1～C5 in the metal nanoparticle of the composition for electrode formation of use is 100%.The carbon skeleton of the organic molecule of chemical modification metal nanoparticle is carbon number 3, the primary particle size contained by metal nanoparticle be the average of the metal nanoparticle in the range of 10～50nm be 80%.Prepare the base material shown in table 17.
Then, base material is not carried out primary coat process, utilize the coating process shown in table 17 below to make composition for electrode formation after film forming is to reach the thickness of 300nm on base material, burn till 30 minutes at a temperature of shown in table 17, base material is formed electrode.
<comparative test 5>
For being formed with in embodiment C1～C35 and comparative example C1～C5 the base material of the electrode obtained, evaluate electric conductivity and the cementability to base material.Electric conductivity is obtained as the specific insulation (Ω cm) utilizing four-terminal method to measure and calculating.Specifically, first the thickness to the electrode after burning till uses SEM (ultramicroscope of society of Hitachi: S800) directly to be measured the thickness of electrode by electrode sections, then use the ratio resistance measurer (Mitsubishi Chemical ロ レ ス タ GP) utilizing four-terminal method, this determinator inputs the thickness of the electrode of above-mentioned actual measurement and measures the specific insulation of electrode.The adaptation of base material is evaluated qualitatively by the adhesive tape of the base material forming electrode tears stripping test, " well " represents situation about peeling off from base material only adhesive tape, " neutral " represents the stripping of adhesive tape and exposes the situation that the state of substrate surface is mixed in, and " bad " represents the situation that substrate surface exposes comprehensively owing to adhesive tape tears stripping.The results are shown in table 18.
[table 15]
[table 16]
[table 17]
[table 18]
As shown in Table 18, being not carried out in comparative example C1～C5 that primary coat processes, conductivity shows 10-6The numerical value of rank, but cementability evaluation all shows " bad " in all examples, and the electrode of formation is peeled off by adhesive tape, and substrate surface exposes.On the other hand, in embodiment C1～C35, having the electric conductivity of excellence, cementability evaluation displays that " well " or " neutral ", processes by implementing primary coat, can confirm that lossless electric conductivity, can improve the adaptation with base material.
<embodiment C36～C41>
Prepare to be scattered in metal nanoparticle 10 weight portion of the about 20nm of the mean diameter shown in table 19 below the composition for electrode formation of the mixed solution of water, ethanol and methanol.It addition, prepare the primary coat coating material of the mixed solution being scattered in water, ethanol and methanol containing material 1 weight portion shown in table 19.ITO is prepared as base material.
Then, on base material, it is coated with primary coat coating material by spin-coating method, is dried 30 minutes in 60 DEG C in an atmosphere.Then on the base material of this coating having carried out primary coat coating material by spin-coating method by composition for electrode formation film forming to reach the thickness of 300nm after, by burning till 30 minutes at 200 DEG C, base material forms electrode.
[table 19]
<comparative test 6>
The base material of electrode is formed for acquisition in embodiment C36～C41, evaluates electric conductivity, reflectance and the cementability for base material.Electric conductivity and the adaptation evaluation for base material are carried out in the same manner as above-mentioned comparative test 5.The reflectance evaluation of film is by ultraviolet-uisible spectrophotometer and the combination of integrating sphere, the reflectance of the film under mensuration wavelength 800nm.It the results are shown in Table 20.
[table 20]
As shown in Table 20, if the ratio of the Nano silver grain contained by metal nanoparticle is less than 75 weight %, then specific insulation rises, the reflectance reduction under 800nm.It addition, if the carbon number of the carbon skeleton of the organic molecule of chemical modification Nano silver grain is more than 3, then specific insulation rises, the reflectance reduction under 800nm.Furthermore, if the proportion of the Nano silver grain that mean diameter is 10～50nm is less than average 70%, then specific insulation rises, the reflectance reduction under 800nm.
[industrial applicability]
According to the present composition, the electrode with silver as main constituent being substantially free of organic thing can be obtained.Therefore, even if use the solaode being formed with above-mentioned electrode throughout the year, conductivity and reflectance also can maintain high level, therefore can obtain the electrode of excellent in stability year in year out.
It addition, according to the present invention, the excellent adhesion of this electrode and base material can be formed, there is the electrode of good texture structure.
According to the present invention, on base material, wet type is coated with work compositions and film forming, can form the electrode of solaode to burn till this easy operation of base material of film forming.So, being not necessarily to vacuum technology during due to film forming, the restriction of technique is little.It addition, according to the present invention it is possible to by burning till formation electrode in a low temperature of less than 400 DEG C, the energy of consumption when electrode is formed therefore can be reduced.
Therefore, the present invention can provide solaode can the electrode of excellent in stability year in year out of life-time service, the operating cost that manufacture equipment of electrode can be greatly reduced.

Claims (10)

1. the composition for electrode formation of solaode, said composition comprises the metal nanoparticle being scattered in disperse medium,
Described metal nanoparticle contains the Nano silver grain of more than 75 weight %,
The protective agent chemical modification of the organic molecule main chain that described metal nanoparticle is had the carbon skeleton comprising carbon number 1～3,
The primary particle size that described metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm,
Containing more than 0.02 weight % and less than the one kind or two or more mixing composition comprised in Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr and Mn of 25 weight % or the metal nanoparticle of alloy composition, and
The amount of metal is 35～50 weight % relative to composition for electrode formation 100 weight %.
2. electrode of solar battery formation compositions as claimed in claim 1, wherein, disperse medium contains the alcohols of more than the water of more than 1 weight % and 2 weight %.
3. electrode of solar battery formation compositions as claimed in claim 1, wherein, disperse medium contain in hydroxyl or carbonyl any one or the two.
4. electrode of solar battery formation compositions as claimed in claim 2, wherein, alcohols is one kind or two or more in methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, isobornyl hexanol, glycerol and erithritol.
5. the composition for electrode formation of solaode, it comprises the metal nanoparticle being scattered in disperse medium,
Described metal nanoparticle contains the Nano silver grain of more than 75 weight %,
The protective agent chemical modification of the organic molecule main chain that described metal nanoparticle is had the carbon skeleton comprising carbon number 1～3,
The primary particle size that described metal nanoparticle contains average more than 70% is the metal nanoparticle in the range of 10～50nm,
Described compositions contains one kind or two or more additive in metal-oxide, metal hydroxides, organo-metallic compound and silicone oil further,
Containing more than 0.02 weight % and less than the one kind or two or more mixing composition comprised in Au, Pt, Pd, Ru, Ni, Cu, Sn, In, Zn, Fe, Cr and Mn of 25 weight % or the metal nanoparticle of alloy composition, and
The amount of metal is 35～50 weight % relative to composition for electrode formation 100 weight %.
6. electrode of solar battery formation compositions as claimed in claim 5, wherein, disperse medium comprises alcohols or containing alcohol solution.
7. electrode of solar battery formation compositions as claimed in claim 5, wherein, metal-oxide is the oxide containing at least one in aluminum, silicon, titanium, chromium, manganese, ferrum, cobalt, nickel, silver, copper, zinc, molybdenum, stannum, indium and antimony or composite oxides.
8. electrode of solar battery formation compositions as claimed in claim 5, wherein, metal hydroxides is the hydroxide containing at least one in aluminum, silicon, titanium, chromium, manganese, ferrum, cobalt, nickel, silver, copper, zinc, molybdenum, stannum, indium and antimony.
9. electrode of solar battery formation compositions as claimed in claim 5, wherein, organo-metallic compound is the metallic soap of the metal in silicon, titanium, chromium, manganese, ferrum, cobalt, nickel, silver, copper, zinc, molybdenum, indium and stannum, metal complex or metal alkoxide.
10. electrode of solar battery formation compositions as claimed in claim 5, wherein, the content of additive is the 0.1～20% of the weight of Nano silver grain.
CN201210443825.1A 2006-06-30 2007-03-20 Form the compositions of electrode of solar battery, method and the solaode of this electrode of use Expired - Fee Related CN103117107B (en)

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